inorganic chemistry

INORGANIC CHEMISTRY

1. INTRODUCTION

THE Report follows the pattern adopted in the last two years. The elements are subdivided into main groups and transition elements, according to the long form of the Periodic Table. Section 2 deals systematically with the chemistry of the elements in the main groups, and Section 3 is concerned with the chemistry of the transition elements. Co-ordination chemistry is reviewed at the beginning of Section 3.

The report of the International Commission on Atomic Weights has been published. The Commission met in July 1957 and agreed that no changes would be recommended in the values for atomic weights approved by I.U.P.A.C. in 1955 (see Annual Reports for 1956, p. 83). However, there are four anisotopic elements for which values derived from physical measurements are regarded by the Commission as more accurate than the values given in the 1955 table. These elements, with atomic weight values from physical measurements, are arsenic (74.92), yttrium (88*91), praseodymium (140.91), and bismuth (208.99). Differences are small, but should be taken into account in work of high accuracy. Serious consideration was also given to the choice of a unified scale for atomic weights, to replace the two oxygen scales. A scale based on the exact number 12 as the assigned mass of carbon-12 appears to offer the best promise of acceptance.l The I.U.P.A.C. Commission on Inorganic Nomenclature at its 1957 meeting adopted the symbol Ar * for argon and Md for mendelevium. The Commission also adopted the names proposed by the discoverers for einsteinium (Es), fermium (Fm), and nobelium NO).^ A table (320 pp.) has been published listing all the radioactive and stable isotopes of the elements, together with a number of their salient features, and is complete to February, 1958.2

Reviews have been published on “ stereochemistry of inorganic molecules and complex ions,” “ high-temperature chemistry,” * “ polarography in non-aqueous solutions,” ‘‘ ortho-salts and maximum oxygen co- ordination,” ‘‘ inorganic high polymers,” and ‘‘ vibrational spectroscopy and its application in structural inorganic chemistry.’’ Other reviews of a more specific character will be mentioned in context.

The quantity of published work in inorganic chemistry has continued to increase. In particular, there have been significant advances in the study

1 2

a

227. 4

E. Wichers, J . Amer. Chem. Soc., 1958, 80, 4121; J. Mattauch, ibid., p. 4125. D. Strominger, J. M. Hollander, and G. T. Seaborg, Rev. M o d . Phys., 1958,80,585. R. J. Gillespie and R. S. Nyholm, Progr. Stereochem., 1958, 2,.261. L. Brewer, X V I Internat. Congr. Pure Appl. Chem., Experaentaa Suppl. VII , 1967,

V. Gutmann and G. Schiiber, Angew. Chem., 1958, 70, 98. R. Scholder, ibid., p. 583. H. Krebs, ibid., p. 615. J. B. Willis, Rev. Pure Appl. Chem. (Australia), 1958, 8, 101.

* The Chemical Society has accepted this recommendation, and the symbol A for argon will no longer be used in its publications,-ED,

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112 INORGANIC CHEMISTRY.

of the organic derivatives of boron, silicon, and phosphorus which are not included in the Report.

2. THE MAIN GROUPS

Group 1.-A monograph has been published on the occurrence and manufacture of lithium and the uses of this metal, its alloys, and compound^.^ The freezing point-composition curve of the system lithium-lithium hydride resembles that of metal-metal halide systems. The f . p. of lithium hydride is 668" & 1" and there is a monotectic at 685" & 1" between 26 and 98 moles yo of the hydride.1° Accurate values for the heats of formation of the crystalline hydrides of lithium, sodium, and potassium have been measured and compared with the corresponding values for the deuterides, the slight differences between the hydrides and deuterides being discussed on the basis of terms involved in the classical calculation of electrostatic lattice energies.ll

The complex Na[PhLiPh] has been known for some years; others are now reported in which sodium is replaced by potassium or czesium and the organic radical is a methyl, n-butyl, phenyl, or para-substituted phenyl group. The preparations, carried out in ether, follow the sequence R,Hg + Li __t RLi; RLi + R,Hg + Na -+ Na[R,Li]. Of the compounds investigated, (di-n-butyl-1ithium)sodium proved to be the strongest metallat- ing agent.12

There is continued interest in the molecular composition of alkali halide vapours (see last year's Report, p. 96) and work has been extended to the hydroxides. The relative abundance of polymeric species in the vapour above alkali fluorides was determined by an analysis of the velocity distribution of the molecules effusing from an isothermal enclosure. The abundance of dimers at a given pressure decreased from lithium fluoride to caesium fluoride, and the dissociation energies of the dimers decreased in the same direction (LiF 58.9, NaF 54.3, K F 47.6, RbF 42.0, CsF 37.8 kcal. mole-l). The trimer of lithium fluoride was observed and had l3 a dissociation energy of 38.3 kcal. mole-l. Similar results were obtained for the alkali-metal chlorides by mass-spectrometric analysis,14 and theoretical calculations agree substantially with experimental results for all the gaseous alkali-metal halides15 Sodium and potassium hydroxides vaporize mainly as dimers in the temperature range 300--450", and energies of dimerization l6 in the gas are 54 and 49 kcal. molew1, close to those obtained for the fluorides. The

10 C. E. Messer, E. B. Damon, P. C. Maybury, J. Mellor, and R. A. Searles, J . Phys. Chem., 1958, 62, 220.

11 S. R. Gunn and L. G. Green, J . Amer. Chew. Soc., 1958, 80, 4782; see also A. F. le C. Holding and W. A. Ross, J . APpZ. Chem., 1958, 8,321. *

12 G. Wittig and F. Bickelhaupt, Chem. Ber., 1958, 91, 865; see also G. Wittig and E. Benz, ibid., p. 873.

M. Eisenstadt, G. M. Rothberg. and P. Kusch, J . Chem. Phys., 1958, 29, 797; see also A. C. P. Pugh and R. F. Barrow, Trans. Faraday Soc., 1958, 54, 671.

14 T. A. Milne, H. M. Klein, and D. Cubicciotti, J . Chem. Phys., 1958, 28, 718; J. Berkowitz and W. A. Chupka, ibid., 1958, 29, 653.

16 T. A. Milne and D. Cubicciotti, ibid., p. 846. 16 R. F. Porter and R. C. Schoonmaker, ibid., 1958, 28, 168; idem, ibid., p. 454;

idem, J . Phys. Chem., 1958, 62, 234; see also L. H. Spinar and J. L. Margrave, Spectro- chim. Actu, 1958, 12, 244.

D. S. Laidler, Roy. Inst. Chem. Monogvaphs, 1957, No. 6.

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ADDISON AND GREENWOOD: MAIN GROUPS. 113

vapour above a fused mixture of sodium and potassium hydroxides contains the species NaK(OH), in addition to monomers and dimers of the individual hydroxides. The stability of the mixed dimer is intermediate between those of its component dimes1'

Finely divided casium reacts with carbon dioxide at 0" to give a blue- black compound of empirical formula Cs2C0,. The compound hydrolyses to an equimolar mixture of cEsium fonnate and caesium hydroxide and evidence is adduced in favour of its formulation as the czsium salt of caesioformic acid, Cs*CO,H.ls

Group 11.-Beryllium oxyacetate, Be,O(OAc) 6, in boiling methanol splits out acetic anhydride intermolecularly to form the methanol adduct of a non-stoicheiometric polymer of approximate composition [Be,O,(OAc)~,-,,~], where m > 2.4 and n > rn. Other aliphatic and cyclic alcohols and also pyridine induce a similar reaction and heterogeneous, often gelatinous mixtures of beryllium oxyacetate and the alcohol or pyridine adduct of the higher basic acetates are slowly precipitated on co01ing.l~ Beryllium oxypropionat e , oxychloroacet ate, and oxybromoacetate, Be,O (RCO,) , (R = Et, CH,Cl, CH2Br) behave analogously.20 An independent study of the reaction of beryllium oxyacetate with methanol and ethanol claims that alcoholysis occurs to give the compounds Be(0R)OAc ; with butanol there was also a polymeric product, formulated as ~B~(OH)OAC,B~(OBU)OAC.~~ Basic beryllium pivalate, acrylate, phenylacetate, and pentapropionate have been prepared and characterized.22 When two monobasic carboxyl groups are replaced by carboxyl groups of dibasic acids, chain polymers of low molecular weight are obtained.

nBe,O(OCO*R), + nR'(COCI), __jc 2nReCOCI + -[Be40(0*C0.R)aX]n-

The monobasic groups RCO, were acetate, propionate, and benzoate, and the dibasic acyl chlorides R'(COCl), were sebacoyl, adipoyl, terephthaloyl,

and isophthaloyl. The compounds were thermally stable -0 at 400" and did not hydrolyse but there was a tendency

/'- for the linear polymers to disproportionate into mono- \ meric basic beryllium carboxylates and cross-linked

polymers -[(Be,0)X3J-.22 -0

( 1 ) x The compound formed between magnesium and acetylene in liquid ammonia has been shown to be

triammineacetylenemagnesium carbide, MgC2,C2H2,3NH,.23 At 2600-2750' silica and calcium metasilicate both react with fused calcium carbide to give silicon carbide, and alumina gives aluminium carbide A&; above 2850" calcium sulphide reacts with carbon to give calcium carbide.%

Dimethyl-calcium, -strontium, and -barium have been prepared from l7 R. F. Porter and R. C. Schoonmaker, J. Phys. Chem., 1958, 62, 486.

I* H. D. Hardt, 2. anorg. Chem., 1957, 292, 53, 224 257. 2o Idem, ibid., 1957, 293, 47. 21 A. I. Grigor'yev, A. V. Novoselova, and K. N. Semenenko, Zhur. neorg. Khim.,

22 C . S . Marvel and M. M. Martin, J. Amer. Chem. SOC., 1958, 80, 619.

2p R. Juza and K. Biinzen, 2. anorg. Chem., 1958, 295, 334.

\ ,C- RLC

L. Hackspill and R. Setton, Compt. rend., 1958, 246, 2430.

1957, 2 2067.

E. L. Lippert and M. R. Truter, J., 1958, 2636.

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the metals and methyl iodide under an atmosphere of helium followed by repeated extraction of the iodine with pyridine. The compounds are unchanged in a vacuum up to 400" but hydrolyse readily and become incandescent when exposed to oxygen or carbon dioxide.25

Barium chloride nitride, Ba2NCl, was obtained by fusing an equimolar mixture of barium chloride and barium nitride. On a phase diagram the compound is seen as a melting-point maximum at 965". The corresponding calcium compound was prepared similarly but strontium chloride and nitride failed to react. Barium chloride nitride was decomposed by cold water but the calcium compound required hot mineral acid for noticeable hydrolysis.26

Group 111.-The chemistry of Group I11 continues to expand rapidly and considerable advances have been reported in the preparation of new compounds of boron and in the determination of structures and stability relations of several compounds of boron, gallium, and indium. Recent lines of development in the chemistry of boron have been reviewed.27

A study of the thermodynamic data for the chlorides of Groups I11 and IV suggests that it is misleading to interpret the instability of thallium(II1) and lead(1v) on the basis of the so-called inert-pair effect and that thc decreasing stability of the group valency is more correctly attributed to a progressive decrease in the covalent bond strength with increasing atomic number in each group.% Stability relations among analogous molecular addition compounds of the Group I11 elements have been extensively reviewed,29 and the stability of complexes of a series of boron esters with pyridine, ammonia, and the ethylamines has been qualitatively related to back co-ordination from oxygen to boron in the acceptor moiety.30

Boron. A new crystalline modification of boron is obtained by pyrolysis of boron tri-iodide on a surface at 800-1000". The rhombohedral crystals are red and have 12 atoms (one icosahedron) in the unit cell, the icosahedra being held in slightly deformed cubic close packing by two types of bond: half of the boron atoms in one icosahedron form conventional single bonds with atoms of other icosahedra and the other kind of bonding involves equilateral triangles of boron atoms, each boron coming from a different icosahedron. This new boron structure is therefore essentially that of the boron framework in the carbide B,&, with the difference that the omission of the chain of three carbon atoms from the octahedral holes results in the closer approach of the icosahedra and the formation of the new triangular b0nds.3~ This is structurally the simplest modification of boron yet prepared. Above 1500" it is transformed into the normal rhombohedral which, though it is the most easily prepared allotrope of this element, has by far the most complicated structure and contains 108 atoms (9 icosahedra) in

25 D. A. Payne and R. T. Sanderson, J . Amer. Chem. SOL, 1958, 80, 5324. 26 P. Ehrlich and W. Deissmann, Angew. Chem., 1958, 70, 656. 27 E. Wiberg, X V I Internat. Congr. Pure Appl. Chem., Experientia Supfil. VII ,

28 R. S. Drago, J . Phys. Chem., 1958, 62, 353. 29 F. G. A. Stone, Chem. Rev., 1958, 58, 101; see also A. P. Kochetkova and V. G.

SO E. W. Abel, W. Gerrard, M. F. Lappert, and R. Shafferman, J., 1958, 2895. 31 L, V. McCarty, J. S. Kasper, F. H. Horn, B. F. Decker, and A. E. Newkirk, J .

1957, 183.

Tronev, Zhur. neorg. Khim., 1957, 2, 2043.

Amer. Chem. SOL, 1958, 80, 2592.

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the unit cell.32 The structure of tetragonal boron has also been elucidated. The 50 boron atoms in each unit cell comprise 4 icosahedra and two individual boron atoms. Each icosahedral boron forms six bonds directed towards the comers of a pentagonal pyramid, five within the same icosahedron and the sixth to an adjacent icosahedron or to an individual boron atom. The resulting framework is continuous in three

A complete single crystal structure of hexaborane, B6H10, shows the molecule to have an approximately pentagonal pyramidal arrangement of boron atoms [shown in planar projection in (2)]. There are four basal bridge hydrogen atoms and, like B5Hg and BloH14, the molecule has no BH, groups.%

0 1 B

t I

0

(3)

0 1

The topological theory of boron hydrides has been extended to include ions and it is predicted that, besides the known ions BH4- and B3H8-, the more stable polyborohydride ions 34 will be Bl2Hl,2-, B,oH142- (cf. BloH1,), BloHl,-, B&ll+, B,H,-, B6H62-, B5Hl0-, and B3H6'. In particular, the close analogy of the filled molecular orbitals of B5H, with those of benzene suggests the possible occurrence of B4H7- and B6Hll+ analogous to the cyclopentadienyl and tropylium ions C,H5- and C,H7+, the BH, group being isoelectronic with the CH group. The expected structure of B,H,- is a trigonal pyramid (3), and B6H11+ is formed simply by adding a proton, H+, to the unoccupied basal bridge position of B6H10 (2).35

A new polyhedron of boron atoms (4) has been found in octaboron octachloride, B,C18, and each boron is joined by a single bond to a chlorine atom as in B,C14.36 Nuclear magnetic resonance establishes that the monoiodide, m. p. 53", and the monobromide, m. p. 34", of pentaborane, B5Hg, are substituted at the apex boron atom and that the monoiodide, m. p. 116" and monobromide, m. p. 105", of decaborane, B10H14, are also apex-substituted. A second monoiodide, m. p. 72", of decaborane, is probably substituted at the B, position.37

An ingenious semicontinuous process for preparing boron and silicon hydrides has been devised.= Applied to the preparation of diborane it

32 J. L. Hoard, R. E. Hughes, and D. E. Sands, J . Amer. Chem. Soc., 1958,80,4507. s8 F. L. Hirshfeld, K. Eriks, R. E. Dickerson, E. L. Lippert, and W. N. Lipscomb,

s4 W. N. Lipscomb, J . Phys. Chem., 1958, 62, 381. s5 Idem, J . Chem. Phys., 1958, 28, 170. s6 R. A. Jacobson and W. N. Lipscomb, J . Amer. Chem. SOL, 1958, 80, 5571. 37 R. Schaeffer, J. N. Shoolery, and R. Jones, ibid., p. 2670. 38 W. Sundermeyer and 0. Glemser, Angew. Chem., 1958, 70, 625.

J . Chem. Phys., 1958, 28, 56.

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involves electrolysis of the molten lithium chloride-potassium chloride eutectic (359") for 10 minutes a t 32 A followed by passage of hydrogen through the catholyte for 30 minutes to convert the liberated lithium metal into lithium hydride. Boron trichloride is then passed through and gives diborane in 40% yield. The cycle can be repeated indefinitely. Silicon tetrachloride was quantitatively converted into silane, SiH,, and dimethyl- silicon dichloride gives dimethylsilane Me2SiH2.38 Sodium borohydride, though insoluble in diethyl ether, is readily soluble in diethylene glycol dimethyl ether (" diglyme ") and this solution, when dropped into a slight excess of boron trifluoride-ether complex in the same solvent, gives a quantitative yield of diborane. This is the most convenient laboratory preparation of diborane yet reported.39 Boron trichloride reacts in a flow system with hydrogen during 30 seconds' contact with an aluminium-copper catalyst a t 450" to give a 54% yield of diborane. Both boron trichloride and diborane were conveniently stored by adsorption on to activated charcoal a t 0" but desorption by pumping was not quantitative.40

Several high-yield interconversions of the boranes have been reported. A hot-cold tube technique has been developed for quantitatively converting diborane into a mixture of tetraborane and B,H,,. Under appropriate conditions either a 95% yield of tetraborane or a 70% yield of B5H11 can be obtained, these yields being higher than any previously reported for these compounds.41 Decomposition of diborane in a silent discharge at 15 kv in the presence of helium produces 40% of B,H,,, 20% of B5H,, 30% of B5H11, and smaller amounts of B6H10 and B9H15. About half the diborane used was transformed after three cycles.42 B5H,! has been converted into tetraborane, B5Hg and hexaborane. Hydrolysis for one minute at 0" gave tetraborane almost quantitatively: B5H11 + 3H,O --t 2H2 + B(OH), + B,H,,. Treatment with bisdimethylaminoborine, (Me,N),BH, at low temperatures gave 50% conversion into B5Hg and also 3.6% of B6Hlo; this represents the most efficient preparation of the rare hexaborane yet reported. Tetraborane a t -78" formed a 1 : 1 adduct with bisdimethylaminoborine, which, when held at -15", gave 25% conversion into B5H,,& Decaborane has less thermal stability than was previously supposed and is rapidly pyrolysed at 200" to a non-volatile polymer of approximate composition

In a closely reasoned set of papers, the diborane diammoniate has been shown not to contain the ammonium ion, as implied by the formulation NH,+[(BH,),NH,]-, but to contain the borohydride ion; its structure 45

(BH10)X.

3O H. C. Brown and P. A. Tierney, J . Amer. Chem. SOC., 1958, 80, 1552. 40 V. I. Mikheyeva and T. N. Dymova, Zhur. neorg. Khim., 1957, 2, 2530, 2539. dl M. J. Klein, B. C. Harrison, and I. J. Solomon, J. Amer. Chem. SOL, 1958, 80.

42 W. V. Kotlensky and R. Schaeffer, ibid., p. 4517. 43 J. L. Boone and A. B. Burg, ibid., p. 1519. 44 B. Siege1 and J . L. Mack, J. Phys. Chem., 1958, 62, 373. 45 D. R. Schultz and R. W. Parry, J . Amer. Chem. SOC., 1958, 80, 4; S. G. Shore

and R. W. Parry, ibid., pp. 8, 12; R. W. Parry and S. G. Shore, ibid., p. 15; S . G. Shore, P. R. Giradot, and R. W. Parry, ibid., p. 20; R. W. Parry, G. Kodama, and D. R. Schultz, ibid., p. 24; see also R. W. Parry, D. R. Schultz, and P. R. Giradot, ibid., p. 1; J. R. Weaver, S. G. Shore, and R. W. Parry, J. Chem. Phys., 1958, 29, 1.

4149.

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is [(NH,),BH,] +BH,-. Reaction of diborane with ammonia therefore results in unsymmetrical cleavage (BH2+ + BH,-) in contrast to the symmetrical cleavage (BH, + BH,) which results from reactions with amines. The monomer BH,-NH, was made by reaction of an ammonium halide with a borohydride (including diborane diammoniate) : MBH, + NH,X _+ MX + BH,*NH, + H,. The reactions of these and related compounds have been studied extensively45 and the Raman spectrum of diborane diammoniate in liquid ammonia furnishes further evidence for the presence of the borohydride i0n.46 Phase diagrams show that diethyl ether forms two complexes with diborane, the expected BH,,Et,O, m. p. -124", and also (BH,),,Et,O, m. p. -1126". Ethyl methyl ether forms only a 2 : 1 complex (BH,),,MeOEt, m. p. - 139", whereas dimethyl ether, tetrahydrofuran, and tetrahydropyran form 1 : 1 c~mplexes.*~ Pressure-composition isotherms indicate that lithium borohydride forms a 1 : 1 adduct with dimethyl, diethyl, and di-isopropyl ethers, and in addition the compounds LiBH4,2Me,0, (LiBH,),,Me,O, and (LiBH,),,Et,O were established and the heats of dissociation of all six compounds determined.48

Diborane reacts with the fluoro-derivatives of ethylene to give complex mixtures of products; fluorine is replaced by hydrogen in the ethylenes and boron appears mainly as BF,, EtBF,, Et,BF, and Et,B.49 Sodium borohydride dissolved in tetraethylene glycol dimethyl ether reacts with vinyl and ally1 bromides to give dialkyldiboranes in 70--80~0 e l d ; e.g., NaBH, + CH,=CHBr + NaBr + +Et,B,H,. Diborane and triphenylboron react at 2 - 4 atm. and 40-100" to give diphenyldiborane, Ph,B,H,, and the same compound can also be obtained by reducing phenylboron dichloride with lithium borohydride: PhBCl, + 2LiBH4 + 2LiC1+ QPh,B,H4 + B?H6. Diphenyldiborane and phenyl-lithium afford lithium phenylborohydride, Li[PhBH,], m. p. 5-9", and this forms 1 : 2 adducts with diethyl ether and dioxax6l

Diborane forms 1 : 1 adducts with O-methylhydroxylamine, MeOeNH,, and its N-methyl derivatives MeOONHMe and MeOoNMe, ; their stability increases with increasing methylation but all evolve hydrogen and form polymers above their m. p., the decomposition being explosive at higher temperatures. The 1 : 1 addition compound between diborane and NN-di- methylhydroxylamine was also prepared by analogous compounds with hydroxylamine itself and N-methylhydroxylamine gave impure products which lost hydrogen explosively even at low temperature^.^^ The complex B2H,,P,H4 formed by the addition of diborane to diphosphine at -78" is more stable to decomposition by elimination of phosphine than is diphosphine

46 R. C. Taylor, D. R. Schultz. and A. R. Emery, J . Amer. Chem. Soc., 1958, 80, 27. 47 H. E. Wirth, F. E. Massoth, and D. X. Gilbert, J . Phys. Chem., 1958, 62, 870. 48 G. W. Schaeffer, T. L. Kolski, and D. L. Ekstedt, J . Amer. Chem. Soc.. 1957, 79,

6912; T. L. Kolski, H. B. Moore, L. E. Roth, K. J. Martin, and G. W. Schaeffer, ibid., 1958,80, 549; J. J. Bums and G. W. Schaeffer, J . Phys. Chem., 1958,62, 380.

49 B. Bartocha, W. A. G. Graham, and F. G. A. Stone, J . Inorg. Nuclear Chem., 1958, 6, 119.

6o T. Wartik and R. K. Pearson, ibid., 1958, 5, 250. s1 E. Wiberg, J. E. F. Evans, and H. Noth, 2. Naturforsch., 1958, 13b, 263, 265. 6r4 D. H. Campbell, T. C. Bissot, and R. W. Parry. J . Amer. Chem. Soc., 1958, 80,

1649, 1868.

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itself, but when the reaction is carried out at room temperature both phosphine and hydrogen are evolved, leaving a defective solid containing boron, phosphorus, and hydrogen. The analogous compIex with boron trifluoride, (BF3),,P2H4, eliminates 53 phosphine above -118".

Pentaborane forms a series of non-volatile, liquid complexes B,H,,%R,NH (n = 2-45) with dimethylamine and diethylamine, and solid complexes B,H,,BR,N with trimethylamine and triethylamine. When these complexes are warmed above 0" a series of reactions occurs with evolution of hydrogen and the breakdown of the pentaborane molecule to form polymers.54 An inorganic Grignard reagent, BloH13MgI, is formed when decaborane reacts with magnesium iodide in ether. The compound hydrolyses to decaborane and yields benzyldecaborane, m. p. 64.6", when treated with benzyl chloride. The compound B,H,,(MgI), was also prepared.65

B10H14 + MeMgl B10H13Mg1 f HZo

B1oH13Mgl + 2PhCHzCI

CH4 + B10H13Mg1 BIOHIO $. Mgl*oH

PhCH,*B,oH13 + MgCIz + PhCHZI

BioH13Mgl f MeMgl + BioHiz(Mgl)Z + CH4

The diphenylboronium cation Ph,B+ has been identified in a solution of diphenylboron chloride in ethyl methyl ketone containing one equivalent of aluminium chloride: Ph,BCl + AlCl, + Ph,B+(solv.) + AlC14-. The solution was bright yellow and the ion is the boron analogue of the diphenyl- carbonium ion Ph,CH+.56 The vapour-phase reactions of trimethylboron with water, hydrogen sulphide, ethylene glycol, and several ortho-substituted phenols were investigated 57 at 200-340". A series of acyloxy-derivatives of boron have been preparedm and their infrared spectra reported.59 A useful review of the infrared spectra of a large number of organoboron compounds has been published and the frequencies of some characteristic groups listed.60 The possible use of arylboronic acids in brain-tumour therapy has stimulated renewed interest in the synthesis of these compounds.61

Tri-N-alkyl-tri-B-chloroborazoles (Alkyl = Me, Et, Bun) were prepared smoothly in 80% yield by the following sequence of reactions (illustrated

G. J. Beichl and E. C. Even, J . Amer. Chem. SOC., 1958, 80, 5344. 64 A. F. Zhigach, Ye. B. Kazakova, and I. S. Antonov, Zhur. obshchei Khim., 1957,

65 B. Siegel, J. L. Mack, J. U. Lowe, and J. Gallaghan, J . Amer. Chem. SOC., 1958,

66 J. M. Davidson and C. M. French, J., 1958, 114. 57 D. Ulmschneider and J. Goubeau, Chem. Ber., 1957, 90, 2733. 58 W. Gerrard, M. F. Lappert, and R. Shafferman, J., 1958, 3648; L. A. Duncanson,

W. Gerrard, M. F. Lappert. H. F'yszora, and R. Shafferman, ibid., p. 3652; see also B. M. Mikhailov and N. S. Fedotov, Izvest. Akad. Nauk S.S.S.R., Otdel. khim. Nauk, 1958, 857; B. M. Mikhailov and T. A. Shchegoleva, ibid., p. 860.

60 M. F. Lappert, J., 1958, 2790, 3256; see also T. P. Povlock and W. T. Lippincott, J . Amer. Chem. SOL, 1958,80,5409.

60 L. J. Bellamy, W. Gerrard, M. F. Lappert, and R. L. Williams, J.. 1958, 2412; see also H. R. Snyder, M. S. Konecky, and W. J. Lennarz, J . Amer. Chem. SOC., 1958, 80, 3611.

6 1 H. R. Snyder, A. J. Reedy, and W. J. Lennarz, ibid., 1958, 80, 835; L. Santucci and H. Gilman, ibid., p. 193; H. Gilman and L. 0. Moore, ibid., p. 3609.

27, 1655.

80, 4523.

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ADDISON AND GREENWOOD MAIN GROUPS. 119

by the methyl derivative) : MeNH, + BCl, + BCl,,MeNH, (m. p. 126-128') in boiling chlorobenzene; BCl,,MeNH, + 2Me3N + 2Me3NHC1 + *Me,N,B,Cl, (m. p. 153-156') in toluene suspension. The triethyl derivative melts at 55-57' and the tributyl at about 30'.62 The three chlorine atoms in the trimethyl derivative can be successively replaced by a variety of alkyl groups by use of the Grignard reaction.63

Diboron tetrafluoride, B2F4, which (unlike B2C14) cannot be made by electrical discharge through the trihalide, has now been prepared in excellent yield by fluorination of diboron tetrachloride with antimony trifluoride. It is a stable gas, m. p. -56", b. p. -34", which decomposes slowly at 200" and is chemically very similar to the chloride.@ The molecule 66 is planar, F,B-BF,. Yields of diboron tetrachloride were improved more than tenfold when a d.c. rather than an a.c. discharge was employed in the preparationF6 and microwave excitation has also been suggested67 as a means of stimulating the decomposition of the trichloride : 2BC13 _t

B2C14 + Cl,. When a silent electric discharge was passed through boron tribromide at low pressures, free bromine and a red solid (BBr), were obtained, and when a glow discharge was used with argon as carrier the products were an amorphous powder BBT,,.,-~.~, the known liquid B,Br4, and the previously mentioned red solid (BBr),. The latter on ammonolysis gave @ the new white substance (B,NH),.

The 1 : 1 and 1 : 2 addition compounds of boron trifluoride with heavy water have been prepared, and their properties compared with those of the mono- and di-hydrates. Deuterium substitution raises the m. p.s by 5.0" and 5.1" respectively, this increase being greater than for any other isotopic pair of compounds yet reported. The influence of deuteration on electrical conductivity and viscosity is consistent with the view that the fused compounds are considerably ionized as D+[BF,*OD]- and D,O+[BF,*OD]- and conduct electricity by normal ionic migration rather than by a chain mechanism.68 Phase studies indicate that boron trifluoride not only forms the familiar 1 : 1 ether complex but also a 3 : 1 adduct (BF,),,Et,O, m. p. -71'. Dimethyl and di-isopropyl ethers form only the known 1 : 1 complexes but ethyl methyl ether and methyl propyl ether form complexes with both 1 and 2 mol. of boron trifluoride. The 2 : 1 and 3 : 1 complexes are less stable than the 1 : 1 but all melt congruently above the b. p. of boron t r i f l~oride.~~ Boron trifluoride forms a stable, white, solid complex with dinitrogen pentoxide which decomposes in inert solvents above 75", is an excellent nitrating agent, and has been formulated 71 as N02+[0,N0 + BF,]-.

hailov and T. K. Kozminskaya, Doklady ARad. Nauk S.S.S.R. , 1958,121, 656.

80, 4515.

62 H. S. Turner and R. J. Warne, Chem. and Ind., 1958, 526; see also B. M. Mik-

6a G. E. Ryschkewitsch, J. J. Harris, and H. H. Sisler, J . Amer. Chern. SOC., 1958,

65 L. Trefonas and W. N. Lipscomb, J . Chem. Phys., 1958, 28, 54. 66 A. K. Holliday and A. G. Massey, J . Amer. Chem. SOC., 1958, 80, 4744. 67 J. W.. Frazer and R. T. Holzmann, ibid., p. 2907; see also R. T. Holzmann and

68 A. Pflugmacher and W. Diener, Angew. Chem., 1957, 69, 777. 6s N. N. Greenwood, J . Inorg. Nuclear Chem., 1958, 5, 224, 236. 'O H. E. Wirth, M. J. Jackson, and H. W. Griffiths, J . Phys. Chem., 1968,62, 871. 71 G. B. Bachman and J. K. Dever, J . AMY. Chem. SOL, 1968, 80, 5871.

A. Finch and H. I. Schlesinger, ibid., p. 3573.

W. F. Morris, J . Chem. Phys., 1958, 29, 677.

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The preparation, thermal stability, and physical properties of complexes of boron trifluoride with numerous ketones have been reported.72 An unusual preparation of boron trifluoride dialcoholates involves the quantitative conversion of trialkyl borates with hydrogen fluoride at 30" : B(OR), + 3HF -+ BF3,2ROH + ROH. The complex RF,,AcOH was likewise formed in good yield when hydrogen fluoride reacted with boric oxide in acetic anhydride.73

The infrared spectra of complexes between aliphatic and aromatic ketones and such electron acceptors as BF,, AlCl,, FeCl,, and ZnC1, show a characteristic lowering of the C=O vibration frequency and this, together with some dipole-moment measurements, is considered 74 to favour the structure R2C=O+BF, rather than [ (R2C=O)2BF2]+ BF4-. Infrared and Raman data on pyridine, quinoline, and isoquinoline complexes of boron trifluoride and aluminium trichloride are also rec0rded.7~ Dipole moments of pyridine and trimethylamine complexes indicate that electron-acceptor power increases 75 in the order BF, < BH, < BCl, < BBr,, the sequence for the halides being the same as that previously obtained from the heats of formation of the complexes. Consistently with this, diphenyl ether forms a 1 : 1 addition compound with boron trichloride but not with boron t r i f l~or ide .~~ Dioxan forms a 1 : 1 complex when mixed with boron trichloride in methylene dichloride; addition of excess of boron trichloride formed the insoluble 3 : 2 complex (BC1,),,2C4H,0, from which the 1 : 1 complex could be recovered by addition of dioxan. Both complexes hydrolyse immediately to boric acid, hydrochloric acid, and dioxan. Boron tribromide formed only the 1 : 1 complex, a white solid less stable than the chloro-compound.77

The electron-acceptor properties of boron trichloride have been reviewed and findings suggesting the presence of the tetrachloroborate ion in some complexes discussed; infrared bands at 670 and 800 cm.-l were assigned to this Alkali-metal tetrachloroborates MBCl, have been prepared by direct addition of boron trichloride to metal chlorides under pressure at high temperatures. Stability increases from potassium through rubidium to c~esium.7~ Alkyl-substituted ammonium tetrachloroborates were formed when boron trichloride was added to an alkylammonium chloride in boiling chloroform, the preparation differing from that of the tri-N-alkyl-tri-B- chloroborazoles (see p. 118) only in the choice of solvent. The five tetrachloroborates investigated all had strong peaks in the region 660-700 cm.-l of the spectrum.80 Tetrachloroborates were also formed when

72 R. Lombard and J. P. StBphan, Bull. SOC. chim. France, 1957, 1369. 7a E. L. Muetterties, J . Amer. Chem. SOC., 1958, 80, 4526. 74 B. P. Susz and P. Chalandon, Helv. Chim. Actu, 1958, 41, 697, 1332; H. Luther,

D. Mootz, and F. Radwitz, J . grakt. Chem., 1957, 5, 242. 76 C. M. Bax, A. R. Katritzky, and L. E. Sutton, J., 1958, 1258; see also idem, ibid.,

p. 1254. 76 R. M. Healy and A. A. Palko, J. Chem. Phys., 1958, 28, 211; see also A. A. Palko,

R. M. Healy, and L. Landau, ibid., p. 214. 77 M. J. Frazer, W. Gerrard, and S. N. Mistry, Chem. and Ind., 1958, 1263. 78 N. N. Greenwood, K. Wade, and P. G. Perkins, X V I Internat. Congr. Pure Afipl.

Chem. (Sect. Chim. min.), Paris, 1957, 491; see also R. H. Herber, J . Amer. Chem. SOC., 1958, 80, 5080, for kinetic evidence.

79 E. L. Muetterties, J . Amer. Chem. SOC., 1957, 79, 6563. 80 W. Kynaston and H. S. Turner, Proc. Chem. Soc., 1958, 304.

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cyclohexylamine or benzylamine reacted with boron trichloride in methylene dichloride a t -78", the simultaneously formed substituted aminoboron dichloride also being isolated: 81 SRNH, + 2BC13 + 2(BC13,RNH,) _t

RNH3+ BC1,- + RNH*BCl,. A study of the dehydration of the metaborates Ca(B0,),,2H20 and

Ca(B0,),,6H20 has led to a re-formulation of these salts as dihydrogen borates, Ca(H,BO,), and Ca(H2B0,),,4H,O, in which boric acid behaves as a monobasic acid. Calcium monohydrogen borate CaHBO, was also prepared and thermally dehydrated to the diborate C S B , ~ ~ . ~ ~ Reaction of " boron acetate " with glycerol does not give the highly strained glycerol borate (5A) as previously thought but a white, amorphous powder formulated as (5B) on the basis of molecular weight, infrared spectra, and the presence of hydroxyl groups.*,

H2C.O O.CH2 I

H2C. 0

H0.C.H 'f3-0- B' H-k-OH

'O-CH, (58) I I /

Aluminium, gallium, indium, and thallium. The physicochemical study of complexes formed between aluminium tribromide and various ethers continues and the conductivity, viscosity, and density of several ternary systems are reported.84 The infrared spectra of many addition compounds of the aluminium trihalides with a variety of ligands have been reviewed,85 and the infrared spectra of 1 : 1 complexes of aluminium trichloride and tribromide with methyl nitrate, nitrobenzene, and several para-substituted nitrobenzenes are interpreted as showing that only one oxygen atom in the nitro-group is involved in bonding to aluminium.86 Ultraviolet absorption spectra and solubility studies indicate weak complex formation between Al,Br6 and pent-2-ene in solution but no solid complex was found down to -23", in contrast to the behaviour in benzene which is a better solvent for A1,Br6 and which forms an incongruently melting complex with it.*'

The existence of univalent gallium in gallium dibromide has been established by Raman spectroscopy, the structure of the (diamagnetic) compound being Ga+GaBr,-, analogous to the dichloride.88 Consistent with this, gallium dichloride, m. p. 172~4"~ and dibromide, m. p. 166-7", are typical molten salts with conductivities similar to that of fused silver nitrate; the physical properties of both compounds were measured over a range of t e m p e r a t ~ r e . ~ ~ The dibromide is dimorphic and can be partly reduced to

81 W. Gerrard and E. F. Mooney, Chem. and Ind., 1958, 1259. s2 H. A. Lehmann, A. Zielfelder, and G. Herzog, 2. anorg. Chew., 1958, 296, 199;

83 W. Gerrard and E. F. Mooney, Chem. and Ind., 1958, 227. 84 Ye. Ya. Gorenbein and V. L. Yivnutel, Zhur. obshchei Khim., 1957,27,20; Ye. Ya.

85 A. Terenin, W. Filimonow, and D. Bystrow, 2. Elektrochem., 1958, 62, 180. 86 P. Gagnaux, D. Janjic, and B. P. Susz, Helv. Chim. A d a , 1958, 41, 1322; see also

see also J. Krogh-Moe, Arkiv Kemi, 1958, 12, 277.

Gorenbein and V. N. Danilova, ibid., p. 858; idem, ibid., 1958, 28, 1387.

idem, ibid., p. 1023, for dipole moments. F. Fairbrother and J. F. Nixon, J., 1958, 3224. L. A. Woodward, N. N. Greenwood, J. R. Hall, and I. J. Worrall, ibid., p. 1505.

8s N. N. Greenwood and I : J. Worrall, ibid.. p . 1680.

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the monobromide, a reaction which goes to completion in the presence of aluminium tribromide : Ga+GaBr,- + 2Ga + ZA12Br6 + 4Ga+AlBr4-.90 The corresponding chloro-complex was prepared similarly and also by direct reduction 91 of molten gallium trichloride with aluminium a t 190" : 2Ga2C1, + 3A1- 3Ga+A1C14- + Ga. The dihalides of gallium are usually prepared by direct reduction of the trihalides with gallium; a new method involves heating gallium metal a t 150" with mercurous or mercuric halides. In the presence of benzene the complexes Ga+GaCl,-,C,H, and Ga+GaBr,-,C,H, were obtained. Addition of hydrogen sulphide to such benzene solutions precipitated only the univalent gallium; hydrogen halide was evolved and gallium trihalide remained in solution : e.g., 2Ga+GaCl,- + H2S _+

G+S + 2HC1+ Ga2Cl,. The sulphide precipitate could not be characterized and contained up to 20% by weight of chlorine.92 The thermal stability of phases occurring in the system Ga-S were re-investigated up to 1300". Digallium disulphide melts at 970" and then decomposes: 3Ga,S2 -F Ga,S, + Ga2S. Crystalline digallium monosulphide disproportionates above 950" (2GsS + Ga,S, + Ga) and a t the same temperature the sesquisulphide loses sulphur: 2GsS, + Ga,S, + QS,. The compound Ga,S, ( i e . , Gas,.,,) is stable up to 1200" and variesg3 in composition from Gas,., to Gastw.

Phase studies indicate that gallium trichloride forms two complexes with pyridine, GaCl,,py, m. p. 126", and GaC13,2py, m. p. 113"; the 1 : 2 complex reverts to the 1 : 1 compound when evacuated. Both complexes form ionic melts and their physical properties, measured over a range of temperatures, have been interpreted on the basis of the formulz [py2GaC1,]+GaC1,- and Cpy2GaC12] +C1-. The piperidine complexes GaCl,,pip, m. p. 134", and GaC13,2pip, m. p. 112", are analogous.94 The heats of formation of piperidine complexes of gallium trichloride and tribromide are greater than those of the pyridine complexes and the first mol. of ligand is added with considerably more evolution of heat than the second. Heats of formation of several other addition compounds of the trichloride were studied and it was also shown that the heats of formation of crystalline complexes of the tribromide were greater than the corresponding heats for complexes of the t r i~hlor ide .~~

An important study of the lower halides of indium has been published. The mono- and di-halides (X = C1, Br, I) were prepared from indium and appropriate amounts of mercurous or mercuric halides at 325400". Phase studies show that indium dichloride does not exist as a compound, and preparations having this stoicheiometry are equimolar mixtures of In2C13 and InCl,. The latter is extracted by a small amount of ether to leave the solid In2Cl,, which is the most stable species in the system and is formulated as (111+)~1nCl~,-, i.e., InC13,31nC1. Further continuous ether extraction of this compound leaves a residue approaching InCl in composition, the

O0 J. D. Corbett and A. Hershaft, J . Amer. Chem. SOL, 1958, 80, 1530. O1 R. K. McMullan and J . D. Corbett, ibid., p. 4761. 92 R. C. Carlston, E. Griswold, and J. Kleinberg, ibid., p. 1532. g3 H. Spandau and F. Klanberg, 2. anorg. Chem., 1958, 295, 300; see also idem,

9* N. N . Greenwood and K. Wade, J., 1968, 1663, 1671. Naturwiss., 1958, 45, 209, for thallium sulphide.

N. N. Greenwood, J. Inorg. Nuclear Chem., 1958, 8, 234.

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ADDISON AND GREENWOOD : MAIN GROUPS. 123

solution phase again containing InCl,. The complex In+AlC14- was prepared by chlorinating a mixture of indium and aluminium with mercury chloride.96 In contrast to gallium, indium didsnot form fluoro-complexes with 13 of a series of 15 cations investigated. However, the known complex (NH4),InF, was formed, and cobaltous fluoride reacted with indium trifluoride in dilute hydrofluoric acid to give the red complex [CO(H,~),]~+[I~F,,H,~]~-. Thermal analysis of the system LiF-InF, showedg7 that the only stable complex was Li,InF,, m. p. 867". Trimethylindium (unlike Al,Me,) is a tetramer and the elucidation of its structure by X-ray analysis reveals the presence of both inter- and intra-molecular methyl bridges of new type?8

The 1 : 1 and 1 : 2 complexes of thallic halides with bidentate ligands B (B = 2,2'-dipyridyl, 1 ,lo-phenanthroline, and ethylenediamine) are uni-univalent electrolytes of the type [B,T1X2] +TlX,- and [B,TlX2] +X- where X = C1, Br, I; gQ cf. the complexes of gallium trihalides with pyridine and piperidine (p. 122). Thallous t-pentyloxide is a tetramer like the lower homologues, implying that these tetramers are structures which can accommodate bulky alkyl groups.l0O The infrared spectrum of cyclo- pentadienylthallium, TlC,H,, indicates a " half-sandwich " configuration of C,, symmetry. Chemical reactions and molecular-orbital calculations suggest lol that the bonding is essentially ionic.

Group IV.-A new scale of electronegativity based on electrostatic force has been proposed and applied in detail lo2 to the study of analogous compounds of C, Si, Ge, Sn, and Pb.

The preparation of graphitic oxide by methods described in the literature is time-consuming and hazardous. A rapid and relatively safe method has been developed in which the graphite is oxidized below 45" with an anhydrous mixture of sulphuric acid, sodium nitrate, and potassium permanganate for less than 2 hour.lo3 Graphitic oxide has the constant overall composition C,04H2 independent of the type of graphite used, and the tentative assign- ment of functional groups mentioned in last year's Report (p. 104) has been confirmed and extended.la Graphite reacts with chlorine at -78" during 500 days; the total uptake is 42% by weight and the anomalous diamagnetism of graphite is completely removed. Finely ground graphite reacts more rapidly than coarsely ground graphite, for which the speed of reaction is strongly dependent on temperature with a maximum at -12". Above 0" absorption of chlorine cannot be detected magnetochemically.lM The system is thus very similar to the graphite-bromine system. Bromine- graphite " compounds " react with chlorine or iodine more rapidly than

96 R. J . Clark, E. Griswold, and J. Kleinberg, J. Amer. Chem. SOC., 1968, 80, 4764. 97 J . E. Roberts and A. W. Laubengayer, ibid., 1967, 79, 5895. 98 E. L. Amma and R. E. Rundle, ibid., 1968, 80, 4141. 9e G. J. Sutton, Austral. J. Chem., 1968, 11, 120.

loo D. C. Bradley, J., 1958, 4780. lol F. A. Cotton and L. T. Reynolds, J. Amer. Chem. Soc., 1958, 80, 269. Io2 A. L. Allred and E. G. Rochow. J. Inorg. Nuclear Chem., 1958, 5, 264, 269.

W. S. Hummers and R. E. Offeman, J. Amer. Chem. SOL, 1958,80, 1339. Io4 J . H. de Boer and A. B. C. van Doom, Proc. k. ned. Akad. Wetenschap., 1968, 61,

R. Juza, P. Janck, and A. Schmeckenbecher, 2. anorg. Chem., 1957, 292, 34. B, 12, 17, 160.

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does graphite itself, apparently because of the formation of interhalogen compounds, such as iodine bromide.lO6 Sodium, unlike its heavier congeners, has previously been thought not to form a lamellar compound with graphite. The compound C,,Na has now been prepared by heating graphite with 3% by weight of sodium in an atmosphere of helium at 200-500" for about 1 hour, and its probable structure deduced on stoicheiometric and X-ray evidence.lo7 Several intercalation compounds of graphite with gallium trichloride and indium trichloride in the presence of chlorine have been studied and compared with analogous compounds formed by aluminium chloride and ferric chloride. The gallium compounds always appeared to have a ratio C1: Ga between 3-2 and 3.4 whereas 108 the ratio for the indium compounds was more nearly 3.0. Established procedures being used, the whole series of graphite-rare earth chloride systems was re-investigated and only yttrium trichloride and gadolinium trichloride found to intercalate consistently and in appreciable quantities.lOg

" Red carbon," prepared by the anhydrous pyrolysis of carbon suboxide, has the composition (C30Jn. X-Ray analysis, paramagnetic resonance absorption, and the nature of the hydrolysis products indicate that it consists of small graphite-like layers about 10 A across in which some of the carbon atoms are replaced by oxygen atoms. The edges of the layers carry functional groupsllo such as -OH, =O, and -CO,H. Some properties of explosive, solid carbon monosulphide have been reported.lll

A stable, dipositive carbonium ion formed by the loss of two chloride ions from a single carbon atom, is produced when trichloromethylpenta- methylbenzene is dissolved in anhydrous sulphuric acid : C,Me5*CC1, + 2H,S04 _+ C,Me5*CC12f + 2HS04- + 2HC1. In accordance with this equation the solution is intensely red, has a van't Hoff i-factor of 5-0, and evolves two mol. of hydrogen chloride when nitrogen is bubbled through, leaving a solution of identical spectrum but having an i-factor of 3. Both solutions on hydrolysis gave quantitative yields of pentamethylbenzoic acid C,Me,*CO,H and the presence of the two highly conducting bi- sulphate ions was demonstrated by measurement of the equivalent con- duc tivi ty.l12

When silver cyanide is electrolysed between silver electrodes in liquid ammonia the cyano-radicals formed dissolve silver quantitatively. With an antimony anode and pyridine as solvent, the new compound antimony tricyanide was formed almost quantitatively. Bismuth behaves similarly, but with arsenic some paracyanogen was f0rmed.1~3 Electrolysis of silver cyanide in liquid ammonia between inert electrodes yields cyano-radicals which react with the solvent to give ammonium cyanide and nitrogen in

lo* R. Juza and A. Schmeckenbecher, 2. anorg. Chem., 1957, 292, 46; see also G. Colin and A. Herold, Compt. rend., 1957, 245, 2294.

I07 R. C. Asher and S. A. Wilson, Nature, 1958, 181, 409. lo8 W. Rudorff and A. Landel, 2. anorg. Chem., 1958, 293, 327. Io9 R. C. Vickery and N. L. Campbell, J . Anzer. Chem. SOC., 1957, 79, 5897.

L. Schmidt, H. P. Boehm, and U. Hofmann, 2. anorg. Chem., 1958, 296, 246. ll1 M. A. P. Hogg and J. E. Spice, J., 1958,4196; see also H. Schafer and H. Wiede-

112 H. Hart and R. W. Fish, J . Amer. Chem. SOC., 1958, 80, 5894. 11* H. Schmidt and H. Meinert, 2. anorg. Chem., 1958, 295, 156, 173.

meier, 2. anorg. Chem., 1958, 296, 241.

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AIIDISON AND GREENWOOD : MAIN GROUPS. 125

addition to small amounts of cyanogen which react with more ammonia to give 113 the dark red 2,3,5,6-tetraiminopiperazine (6) :

H N

N r C CEN HN=C C=NH HlN- C- C E N / \

NEC CEN HN=C, ,C=NH H,N-C-C=N

H

H-NH-H

I I - I I I

(6) 17) H-NH-H' N

Further evidence from the physical and chemical properties of the hydrogen cyanide tetramer is adduced 114 to support the diaminomalonodinitrile structure (7). Commercial cyanuric chloride has been fluorinated with mixed antimony chlorofluorides under various conditions to give 115 a 71% yield of (CNF),, m. p. -38", b. p. 74"; a 24% yield of C3N3F,C1, m. p. 23", b. p. 113"; or a 20% yield of C3N,FC1,, m. p. 2", b. p. 155". Thiocyanogen trichloride, formed by reaction of thiocyanogen with excess of chlorine, is considered on the basis of chemical and spectroscopic evidence to be the sulphenyl chloride C1N=CC1*SC1.ll6 Equimolar portions of thiocyanogen and chlorine in an inert solvent give monomeric thiocyanogen monochloride, ClSCN, rather than the previously reported inert polymeric species. The monomer adds immediately to olefins giving 2-chloroalkyl thiocyanates.ll7

A quadrivalent silicon complex with acetylacetone [Si(acac),]Cl,HCl has been shown conclusively to be hexaco-ordinated and octahedral by its resolution into optical enantiomers.lls The acid SiMeEtPh*C,H,*CO,H-$ (m. p. 99.5") has also been resolved and this is the first reported resolution of a quadricovalent silicon compound containing a single asymmetric silicon atom. Despite the apparent accessibility of 3d-orbitals on the silicon atom, the acid did not racemize either at 100" in the molten state or in 5% aqueous methanolic potassium hydroxide at room temperature.llg Hydrolysis of the methyl ester of silicic acid in conductivity water has given solutions of pure water-soluble orthosilicic acid H,SiO, ; the conductimetrically determined dissociation constant 120 u7as 1-24 x

Disiloxane, (SiH,),O, reacts with Me,Al,Br, to give the volatile electron- deficient compound Me,Al,(O*SiH,),, m. p. 42", which slowly decomposes with loss of silane at room temperature. Corresponding reactions with the aluminium trihalides give polymeric products (SiH,-OA1X,)n.121 Chloro- methoxytrichlorosilane ClCH,*O-SiCl, has been prepared both by direct chlorination of methoxytrichlorosilane and by reaction of silicon tetrachloride with formaldehyde, and its physical properties and chemical

at 25".

11* P. S. Robertson and J. Vaughan, J . Amer. Chem. SOC., 1958, 80, 2691. 115 A. F. Maxwell, J. S. Fry, and L. A. Bigelow, ibid., p. 548. 116 R. G. R. Bacon, R. S. Irwin, J. McC. Pollock, and A. D. E. Pullin, J. , 1958, 764. 117 A. B. Angus and R. G. R. Bacon, ibid., p. 774; R. G. R. Bacon and R .S. Irwin,

11* S. K. Dhar, V. Doron, and S. Kirschner, J . Amer. Chem. SOC., 1958, 80, 753. llS C. Eaborn and C. Pitt, Chem. and Ind., 1958, 830. 120 R. Schwarz and W. D. Miiller, 2. anorc. Chem., 1958, 296. 273.

ibid., p. 778.

lZ1 W. A. Kriner, A. G. MacDiarmid, an&E. C. Evers, J. Amer. Chem. SOC., 1958, 80, 1546.

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reactions reported.122 In an attempt to increase the electron-donor properties of the oxygen atom in disiloxane its methyl derivatives were prepared. Boron trifluoride and trichloride do not form stable complexes with these compounds even at -78" but cleave the Si*O*Si group, e.g., (MeSiH,),O + BF, _+ MeSiH,F + MeSiH,*O*BF,. The latter compound then decomposes spontaneously : 3MeSiH2*O*BF, __t 3MeSiH,F + BF, + B,O,. Boron tri-iodide and trimethylboron do not react but hydriodic acid also cleaves the Si*O*Si group. No donor properties were exhibited lZ3 by 1,l'-dimethyldisilthiane (MeSiH,),S. Reaction of boron trichloride with cyclosiloxanes (R,SiO), results initially in ring opening (a) followed by rapid disproportionation on attempted distillation (b ) . The tris(dialky1chloro- siloxy)boranes further disproportionate (c) into products which, though more stable, can in turn be disproportionated by distillation (a) into the original cyclosiloxane and dialkyldichlorosilanes : 124 e.g. :

a b

C d (R,SiO), + 3BC13 __t 3RZSiCI*O.BCI, __t 2BC13 + (R,SiCI.O),B

2(R,SiCI*O),B _I_t BzOs + 3(RzSiCI),O (R,SiO), + 3R,SiCI,

The effect of methyl-substitution in the silyl group on the donor properties of nitrogen in the silylamines has been studied and many new compounds prepared. The Si-methylated silylamines are comparatively weak ligands but the NN-dimethylsilylamines are much stronger and form adducts such as BMe,,Me,N*SiMe, and BMe,,Me,N*SiH,Me. In some systems the Si-N bonds were ~1eaved. l~~ NN'-Bis(trialkylsily1) hydrazine compounds, R,Si-NH*NH*SiR,, and silyl esters of perchloric acids, R,Si*O*ClO,, have been reported.126

The synthesis and properties of inorganic compounds of germanium have been reviewed.12' Germanium cyanides have formerly only been known with one cyano-group in the molecule; germanium tetracyanide has now been made by reaction of the tetraiodide with silver cyanide in benzene. It is yellow, decomposes above 80°, and is rapidly solvolysed by water or alcohols.128 A stable complex GeC1,,2py, m. p. 207-214" (decomp.), is reported but the corresponding adduct with diethylaniline could not be made.129 Germane was obtained in 80% yield by reducing the tetrachloride with lithium tri-t-butoxyaluminium hydride Li[(ButO),AIH], but lithium aluminium hydride itself, which reduces stannic chloride smoothly to stannane, gave unsatisfactory results owing to the preferential formation of germanium d i ~ h l o r i d e . ~ ~ ~ (Reduction of lead tetrachloride with lithium

122 R. E. Frost and E. G. Rochow, J . Inorg. Nuclear Chem., 1958, 5, 201, 207. 123 H. J. EmelCus and M. Onyszchuk, J., 1958, 604; H. J. EmelCus and L. E.

Smythe, ibid., p. 609. 124 P. A. McCusker and T. Ostdick, J . Amer. Chem. SOC., 1958, 80, 1103; see also

W. Gerrard and J. A. Strickson, Chem. and Ind., 1958, 860. 125 E. A. V. Ebsworth and H. J. EmelCus, J., 1958, 2150; see also M. Becke-

Goehring and G. Wunsch, Annalen, 1958, 618, 43. 126 U. Wannagat and W. Liehr, Angew. Chem., 1957, 69, 783, 783. 127 H. Nowotny and A. Wittman, X V I Internat. Congr. Pure APPl. Chem.,

Experientia Suppl. VII , 1957, 239. 12* W. Menzer, Angew. Chem.. 1958, 70, 656. lZ0 E. W. Abel, J. , 1958, 3746. 130 S. Sujishi and J. N. Keith, J . Amer. Chem. SOC., 1958, 80, 4138.

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aluminium hydride yielded only metallic lead.131) The new compound hexamethyldigermane Me3Ge*GeMe3 has been prepared in 74% yield by reducing trimethylgermanium bromide with molten potassium, and the reactions of this compound and its silicon and tin analogues ~ t u d i e d . 1 ~ ~

Conductimetric titration of sodium in liquid ammonia with stannane demonstrates the formation of the mono- and di-sodio-derivatives, SnH3Na and SnH,Na,. The former decomposes at -63" in the absence of ammonia but reacts in solution with alkyl iodides to give alkylstannanes, RSnH,. The disodio-derivative is fairly stable at 0" in the absence of ammonia, does not react with methyl iodide, and regenerates stannane when treated with ammonium chloride in ammonia: SnH,Na, + 2NH,C1 __t SnH, + 2NH, + 2NaC1.131 Tin tetrahalides react with ammonia to give the corresponding ammonium halide and ammonobasic tin ( IV) halides SnX (NH,),, where X = C1, Br, I. The complex (NH,),[SnCl,(NH,)J was also isolated and the thermal decomposition of these compounds studied.133 Heats of formation and physical properties of 1 : 2 complexes of stannic chloride with organic ligands containing oxygen or nitrogen are reported.la

The recent chemistry of organotin compounds has been re~iewed.l3~ The alkoxides of tin were prepared by adding ammonia to a mixed solution of stannic chloride and the appropriate alcohol in benzene: SnCl, + 4ROH + 4NH3 + Sn(OR), + 4NH4C1.l3, However, an independent investigation found this reaction unsuitable for the preparation of the pure alkoxides and the preferred method was by alcohol interchange involving the isopropoxide isopropyl alcoholate, Sn2(OPri)8,2PriOH, which was itself obtained by a 4-stage synthesis involving the double alkoxide NaSn,(OEt), and t-pentyl alcohol as intermediates.137 The properties of the alkoxides prepared in this way differ somewhat from those obtained by the ammonia method.

The hexafluoroplumbates of the alkali metals are well known. Those of the alkaline-earth metals have now been prepared, e.g., by direct fluorination of the corresponding plumbates MPbO,. The compound BaPbF, has the hexagonal, BaGeF,-type lattice with discrete PbFG2- anions. The strontium compound is tetragonal and has one-dimensional chains of linked PbF,- octahedra and individual fluoride ions. CaPbF, has the cubic Re0,-type structure with an ordered distribution of Ca2+ and Pb4+ on the cation sites.138 In an attempt to prepare covalent borohydrides of tin and lead it was found that tetramethyl-tin and -lead do not react with diborane but do so vigorously with lithium aluminium hydride to give solid intermediates of the type Me,Sn(BH,), and Me,Pb*BH, which rapidly decompose

lal H. J. EmelBus and S. F. A. Kettle, J. , 1958, 2444. 133 M. P. Brown and G. W. A. Fowles, J. , 1958, 2811. 133 E. Bannister and G. W. A. Fowles, J. , 1958, 751, 4374. ls4 S. T. Zenchelsky and P. R. Segatto, J . Amer. Chem. Soc., 1958, 80, 4796; T.

la5 G. J. M. van der Kerk, J. G. A. Luijten, and J. G. Noltes, Angew. Chem., 1958,

ls6 A. Maillard, A. R. J. Deluzarche, and J. C . Maire, Bull. SOC. chim. France, 1958,

13' D . C. Bradley, E. V. Caldwell, and W. Wardlaw, J . , 1957, 4775.

Sumarakova and I. Litvyak, Zhur. obshchei Khim., 1957, 27, 837, 1125.

70, 298.

853, 855.

R. Hoppe and K . Blinne, 2. anorg. Chem., 1958, 293, 251.

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in the presence of lithium aluminium hydride to the metals, hydrogen, and a mixture of methylboranes and MeA1(BH4)2.139 The reactions of tetramethyl-lead and trimethyl-lead chloride with alkali metals in liquid ammonia have been investigated. The anion PbMe,- is first formed; this reacts with sodium and lithium to give dimethyl-lead but with potassium all three methyl groups are removed and lead imide, PbNH, is obtained, the difference in behaviour being ascribed to solubility effects.140

Group V.-Nitrogen. Thirteen papers were read at a Symposium on '' recent aspects of the inorganic chemistry of nitrogen," 141 and reviews have appeared on the orbitals used in valency bonding in nitrogen compounds,l& and the spectroscopic and chemical properties of active nitrogen.lG

Thermal analysis has established the existence of the compound SiC14,2NOCl.144 Nitrosyl azide, NO-N,, m. p. --57', is obtained as an unstable, volatile yellow compound by the low-temperature reaction of sodium azide or hydrazoic acid with nitric acid or nitrosyl compounds such as nitrosyl chloride or nitrosylsulphuric acid. It decomposes even at -50" into nitrous oxide and nitrogen.145 The history of " violet-blue sulphuric " acid formed in the nitric oxide catalysed synthesis of sulphuric acid is reviewed. The colour is ascribed to a nitric oxide addition compound of nitrosylsulphuric acid, N2O2+HSO4-, and the chemistry of the ion N,02+ is developed. It has two interconvertible isomeric forms, one blue and one carmine red. I' Blue phosphoric " and " violet hydrofluoric " acids can be obtained similarly by adding nitric oxide under pressure to nitrosylphos- phoric and nitrosylhydrofluoric acids.lM

The chemistry of nitryl fluoride, NO,F, and nitronium compounds has been reviewed,l*' and the microwave spectrum of nitryl chloride establishes that it is a planar molecule like the fluoride with chlorine and oxygen atoms at the comers of an isosceles triangle ClN0,.14* The physical and chemical properties of nitryl chloride have been re-investigated and its reaction as a chlorinating agent was shown to be due to small amounts of water present in the organic solvents used.149 In the presence of nitrogen dioxide, chlorine dioxide and nitrosyl chloride react completely according to the equation 2NOC1+ ClO, + N02C1 + NO, + CI,, and the reaction has been the subject of a detailed kinetic study.lW The formation of nitryloxy chloride, NO,Cl, by the reaction of chlorine dioxide or dichlorine oxide with nitrogen dioxide or pentoxide has been investigated under a variety of conditions. Pure NO,Cl is a white solid, melting at 107' to a pale yellow liquid which boils

13s A. K. Holliday and W. Jeffers, J . Inorg. Nuclear Chem., 1958, 6, 134. 140 A. K. Holliday and G. Pass, J., 1958, 3485. 141 Chem. SOC. Special Publ., 1957, No. 10. 142 W. J. Orville-Thomas, Chem. Rev., 1957, 57, 1179. 143 K. R. Jennings and J . W. Linnett, Quart. Rev., 1958, 12, 116. 144 C. Devin and R. Perrot, Comfit. rend., 1958, 248, 950. 146 H. W. Lucien, J . Amer. Chem. SOC., 1958, 80, 4458. 146 F. Seel and H. Sauer, 2. anorg. Chem., 1957, 292, 1; F. Seel, ref. 141, p. 7. 14' G. Hetherington and P. L. Robinson, ref. 141, p. 23. 14* D. J. Millen and IC. M. Sinnott, J., 1958, 350, llS M. J. Collis, F. P. Gintz, D. R. Goddard, E. A. Hebdon, and (in part) G. J.

Minkoff, ibid., p. 438; F. P. Gintz, D. R. Goddard, and (in part) M. J. Collis, ibid., p. 445.

150 H. Martin and E. Kohnlein, 2. phys. Chem. (Franhfwt), 1958, 17, 375.

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ADDISON AND GREENWOOD : MAIN GROUPS. 129

at 18". It is hydrolysed 151 quantitatively by sodium hydroxide to sodium nitrate and hypochlorous acid: NO,Cl + NaOH + NaNO, + HOC1.

The chemistry of dinitrogen tetroxide has been reviewed 15, and a rigorous evaluation of existing data on the NO,-N,O, equilibrium has shown that dissociation is far less in the liquid than in the gas, so that the liquid can be regarded153 as a dilute solution of NO, in N204. The ultraviolet spectra of N,04 in hexane or cyclohexane closely resemble the spectrum of the vapour. With non-aromatic solvents the extinction coefficient decreases with increase in dipole moment of the solvent and there is a decrease in the wavelength of maximum absorption determined largely by the donor properties of the solvent, suggesting that partial electron-transfer occurs rather than the formation of discrete molecules of complex. In aromatic solvents, where the type of electron interaction is different, lmX. is unchanged but the extinction coefficient increases with increasing x-donor strength.lm The occurrence 155 of multibanded spectra in solutions of dinitrogen tetroxide is due to the presence of moisture in the solvents. The volume changes on mixing dinitrogen tetroxide with eleven organic liquids have been correlated with the electron-donor properties of these liquids and compared with corresponding data for mixtures of sulphur dioxide with organic liquids.lM The explosive oxidation of acetonitrile by dinitrogen tetroxide in the presence of indium is reported.16' The fact that the tetroxide in ether reacts with olefins in the presence of iodine to give 2-nitro- alkyl iodides is taken as further evidence for the radical mechanism of addition of dinitrogen . tetroxide to double bonds. Acetylenes (e.g. , P h G C H ) yield l-iodo-2-nitroethylenes (e.g., PhCI=CH*NO,)

Vapour pressures at 0" for the system D20-N,05 have been measured, the total vapour-pressure curve being similar to the one obtained with water. The vapour pressure of pure liquid deuterium nitrate (15.03 mm. at 0.) is 7% higher than that for nitric acid but the heats of vaporization of the two liquids and the extent of their self-dissociation are similar.159 Conductivity and transport numbers of alkali-metal nitrates in anhydrous nitric acid have been determined. Electrode reactions occurring during electrolysis of these solutions are NO2+ + e- __t NO, and NO,- -+,

NO,+ + +02 + 2e-. The transport numbers of NO,+, NO,-, and water in nitric acid are normal, showing that there is no significant contribution by chain conductance in this solvent.lW Studies of the ultraviolet spectra of nitrous acid in aqueous perchloric acid continue and have led to equilibrium constants for reactions involving the formation of NO+ and

161 H. Martin, Angew. Chem., 1958, 70, 97. 152 C. C. Addison and B. J. Hathaway, ref. 141, p. 33; P. Gray, Roy. Inst. Chem.

153 P. Gray and P. Rathbone, J., 1958, 3550. 154 C. C. Addison and J. C. Sheldon, J. , 1958, 3142. 155 A. I?. Altshuller, D. Stephens, and C. M. Schwab, J . Phys. Chem., 1958, 62, 607;

156 C. C. Addison and B. C. Smith, J., 1958, 3664. 157 C. C. Addison, J. C. Sheldon, and B. C . Smith, Chem. aBd Ind., 1958, 1004. l5* T. E. Stevens and W. D. Emmons, J . Amer. Chem. SOC., 1958, 80, 338. 168 J. G. Dawber and P. A. H. Wyatt, J., 1958, 3636. 160 W. H. Lee and D. J . Millen, J.. 1958, 2348.

Monographs, 1958, No. 4.

see also A. P. Altshuller, I. Cohen, and C. M. Schwab, ibid., p. 621.

REP.-VOL. LV E

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N202.161 Nitroxyl, H-N=O, has been detected for the first time by its infrared spectrum; it is formed during the photolysis of methyl nitrite in solid argon at -2253°.162

The halogen derivatives of ammonia have been reviewed.16, A re- investigation of the reaction between liquid ammonia and bromine at -78" has shown that there is an equilibrium between the yellow brornamine, which could be isolated pure, and a violet compound NBr3,6NH3. Nitrogen tri-iodide forms an adduct with silver amide in liquid ammonia, NH,,AgNH,, but with sodium or potassium amide it reacts with liberation of nitrogen: NI, + 3MNH, + N, + 3MI + 2NH3.1m

The oxidation of hydrazine in aqueous solutions has been reviewed and a monograph covering the manufacture and organic chemistry of hydrazine and its use as a reducing agent has also been p~b1ished . l~~ Direct reduction of nitrogen trifluoride by metals a t 375" leads to tetra- fluorohydrazine, N,F,; it boils at -73", has a critical temperature of 36", and has been characterized by analysis and molecular weight.165 The infrared spectrum of the unusual hydrazine derivative (N2H4)3(HI)2 indicates that it is best formulated as (N,H,+I-),,N2H4. Attempts to prepare anhydrous hydrazonium di-iodide were unsuccessful but led to the new hydrate N2H612,2H20.166 The hydrazine-NN-disulphonate (9) and -trisul- phonate (10) were prepared by treating potassium imidodisulphonate (8) with hydroxylamine-0-sulphonic acid and then with pyridine-sulphur trioxide :

HPN.0.SO.H PY-SOa HN(SO3K)Z ___l_t H,N0N(SO3K)2 ____t KO3S*NH0N(SO3K)z

(8) (9) (10)

The hydrazinetetrasulphonate (13) was prepared from the NN'-disulphonate (ll), via the unstable azodisulphonate (12) :

ClSOjK NaOCl N,H, -+ KO,S*NH*NH*SO,K ____t [KO3S*N:N*SO3K] __+ (KO&)zN*N(S03K)z

( 1 1 ) (12) (13)

The hydrolysis and redox reactions of these compounds and others prepared by cation exchange were investigated.16' Hydrazinedisulphamide, H,N*SO,*NH*NH*SO,*NH,, was prepared by reaction of hydrazine with sulphamyl chloride (NH,*SO,Cl) in acetonitrile; it melts a t 111" with decomposition.16*

Phosphorus. Work on the lower hydrides of phosphorus mentioned in last year's Report (p. 108) has been extended to a study of the decomposition of diphosphine in liquid ammonia.169

161 C. A. Bunton and G. Stedman, J., 1958, 2440; T. A. Turney and G. A. Wright, J., 1958, 2415.

162 H. W. Brown and G. C. Pimentel, J. Chew. Phys., 1958, 29, 883. 163 J. Jander, E. Kurzbach. and E. Schmid, ref. 141, p. 65; J. Jander and E. Kurz-

bach, 2. anorg. Chem., 1958, 296, 117; J. Jander and E. Schmid, ibid., 1957, 292, 178. 164 W. C. E. Higginson, ref. 141, p. 95; R. A. Reed, Roy. Inst. Chem. Monographs,

1957, No. 5. 165 C. B. Colburn and A. Kennedy, J . Amer. Chem. SOC., 1958, 80, 5004. 166 E. C. Gilbert and J. C. Decius, ibid., p. 3871. 167 A. Meuwsen and H. Tischer, 2. anorg. Chem., 1958, 294, 282. 168 R. Appel and G. Berger, Chem. Bey., 1958, 91. 1339. 169 E. H. Street, D. M. Gardner, and E. C. Evers, J . Amer. Chem., SOC., 1958, 80,

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Transport measurements in anhydrous phosphoric acid (m. p. 42.35") have established that the abnormally high electrical conductivity of this compound (4.68 x ohm-1 cm.-l at 25") is due to a proton-switch mechanism involving the (dihydrogen phosphate) ion H2P04-. Addition of boron trifluoride to form the complex BF3,H3P04 decreases the amount of hydrogen bonding in the liquid and lowers the viscosity of the system fourfold. The conductivity simultaneously diminishes to an even greater extent owing to the elimination of the chain mechanism. Trideutero- phosphoric acid, m. p. 46.0", behaves ~imi1arly.l~~

The structural chemistry of condensed phosphates has been reviewed and the properties of each group of salts described in detail.171 There is also a review on the paper chromatography of inorganic phosphorus com- p o u n d ~ . ~ ~ ~ The two forms of sodium triphosphate Na5P301, are enantio- morphic, with a transition temperature of 417" & The crystal structure of the low-temperature form has been determined; the P3OlO5- ions have a twofold axis of symmetry (14) and the Na+ ions are co-ordinated by oxygen atoms in distorted octahedral arrangements which form channels parallel to the b axis and sheets parallel to the (101) plane.17* The Raman spectrum of fused sodium diphosphite, Na3HP205,12H20, at 65" differs from that of sodium pyrophosphite and contains lines ascribable to P-P and P-H vibrations. The structure of the anion is 175 therefore (15). The cyclic trimetaphosphate anion reacts with aqueous ammonia at pH 12

to give the monoamidotriphosphate ion (16) which was isolated as its dibariuin salt. High-resolution nuclear magnetic resonance confirms the three chemically different environments of the phosphorus atoms in the ion ,176

O*PO,*O-PO,*O~PO, 4- 2NH3 = NH2 -t [P03.0*P02*O*P0,*NH,]4-- [ I I 1 3 - (16)

Keaction of phosphoryl chloride with phosphorus pentoxide at 200" gives pyrophosphoryl tetrachloride, P203Cl,, m. p. - 16.5", and trimeta- phosphoryl chloride, P306c13 (17). Small amounts of polyphosphoryl chlorides PnO(2n-llCl(r8,. 2) (n = 4,5,6) are also formed.177 Pure dichloro- phosphoric acid, m. p. -28", has been prepared by the controlled

170 N. N. Greenwood and A. Thompson, Proc. Chem. SOC., 1958, 352. 171 E. Thilo, Acta Chim. Acad. Sci. Hung., 1957, 12, 221; &err. Chem.-Ztg., 1958,

172 H. Hettler, J . Chromatog., 1958, 1, 389. 173 G. W. Morey, J . Amer. Chem. Soc., 1958, 80, 775. 174 D. R. Davies and D. E. C . Corbridge, Acta Cryst., 1958, 11, 315. 175 M. Baudler, 2. anorg. Chem., 1957, 292, 325. 176 0. T. Quimby and T. J. Flautt, ibid., 1958, 296, 220. l7' H. Grunzc, ibid., p. 63.

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hydrolysis l78 of pyrophosphoryl tetrachloride at - 60" : Cl,PO*O*POCl, + H20 + 2HP0,C12. The structure of the compound P40&110 (see Annual Reports, 1956, 53, 96) has been investigated by chemical and spectroscopic

methods; these indicate the presence of a c1 CI CI C I CI P-P bond, and the linear formulation (18) I \ I I I

o=p-o-~-P-o--~=o is preferred 179 to a cyclic structure. CI I CI CI / \ CI CI (I8) The addition compound GaBr3,POBr3,

m. p. 154", is less stable than the corresponding chloro-complex, POCl,+GaCI,-, but otherwise has similar properties and is considered to contain the new non-metal cation POBr2+. Physical properties of the two compounds digallium hexabromide and phosphoryl bromide are also reported.180 The infrared spectra of several addition compounds of phosphoryl halides and triphenylphosphine oxide with metal halides have been interpreted in terms of co-ordination through the oxygen atorn.ls1 A single-crystal analysis of the complex SbC1,,POC13 indicates that the antimony atom is surrounded by a square pyramid of chlorine atoms, the sixth octahedral position being occupied by the oxygen of the tetrahedral POC13 molecule.ls2 It seems probable therefore that, depending on the electron acceptor involved, the phosphoryl halides can form addition compounds either by halide-ion transfer or by co-ordination through the oxygen atom. Tetramethyl- and tetraethyl-ammonium chloride form solvates with arsenic trichloride but not with phosphoryl chloride, suggesting that the latter is the weaker chloride-ion acceptor. Solvates with SeOC1, were reported a t the same time.ls3

Vapour-density measurements between 65" and 180" show that gaseous phosphorus pentabromide is completely dissociated, the heat of dissociationls* of the solid into gaseous tribromide and bromine being 26-5 kcal. mole-1. Bond isomerization between ionic and covalent forms of the mixed phosphorus halides is reviewed. The activation energy 185 for the transformation of covalent PC1,F into ionic PCl,+F- is 10.6 kcal. mole-l. The compound PBr4+PF6- was prepared by fluorination of phosphorus pentabromide with arsenic trifluoride and its properties compared with those of the analogous complex PC1,+PF6- (Ann. Reports, 1956, 53, 96); both sublime a t 135" and are isomeric with gaseous PX,F, (see also Ann. Reports, 1957, 54, 114, for AsC14+PF6-) Addition of bromine to phosphorus trichloride in arsenic trichloride yields PCl,+ [PCl,Br]- and arsenic tribromide. The constitution of the complex was established by fluorination with arsenic trifluoride ; this reacts only with the hexa-co-ordinated phosphorus anion, yielding

178 H. Grunze and E. Thilo, Angew. Chem., 1958, 70, 73. 179 R. Klement and E. Rother, Naturwiss., 1958, 45, 489. I80 N. N. Greenwood and I. J . Worrall, J . Inorg. Nuclear Chem., 1958, 6, 34. 181 J C. Sheldon and S. Y. Tyree, J. Amer. Chem. SOC., 1958, 80, 4775. 182 I. Lindqvist and C. I. BrandCn, Acta Chem. Scand., 1958, 12, 134. 183 M. Agerman, L. H. Anderson, I. Lindqvist, and M. Zackrisson, ibid., p. 477;

184 G. S. Harris and D. S. Payne, J., 1958, 3732. 186 L. Kolditz, 2. anorg. Chem., 1957, 298, 147. 186 L. Kolditz and A. Feltz. ibid., p. 155.

see also I. Lindqvist, ibid., p, 135.

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PCl,+PF,--, whereas the complex [PCl,Br] +PF6- would have resulted had the complex been [PC13Br] +PC16-.

The polymeric compound (HN=P-NH,), which can be regarded as the imide-amide of metaphosphorous acid (O=P-OH), has been prepared by the reaction of ammonia with an ether solution of phosphorus trichloride at -20": PCl, + 5NH, __t NH=P*NH, + 3NH4C1. Other reactions occurring in the system are reviewed and various derivatives of the imide- amide prepared.188 Bistrifluoromethylphosphorus chloride reacts similarly in both the vapour and the liquid phase: (CF,),PCl + 2NH,- (CF,),P*NH, + NH,C1. With primary and secondary amines, analogous low-melting, volatile liquids are obtained, e.g., (CF,),P*NHMe, (CF,),P*NMe,, and (CF,),P*NHPh. Hydrolysis and other reactions of these compounds were studied, and their infrared spectra measured for characterization.lsS The tendencies of phosphorus and antimony trichlorides and pentachlorides to form complexes were examined by using trimethylamine, triethylamine, and trimethylphosphine as reference ligands. Various 1 : 1 and 1 : 2 complexes were formed ; phosphorus pentachloride was reduced'b y trimethyl- and triethyl-amine and there was no reaction between triethylamine and phosphorus t richloride or be tween t rimet hylphosphine and phosphorus pentachloride. Phosphorus trichloride and antimony trichloride also formed 1 : 1 complexes with trimethylarsine but the pentachlorides were reduced to the trichlorides with simultaneous formation of trimethylarsenic dichloride, Me,AsCl,. Trimethylstibine reduced both the tri- and the pentachloride to the elements with formation of Me,SbCl, in each case, e.g.,lgo 2SbC1, + 3SbMe, __t 3Me3SbC1, + 2Sb.

A review has appeared on the chemistry of compounds which contain the C-P bond.lgl A series of unexpectedly stable triphenylphosphonium salts Ph,PH+X- have been prepared and characterized by their spectra (X = C1, ClO,, I, SbCl,, FeCl,, FeBr,, +SnCl,, 4SnBr,).lg2 Several dimethyl- arsinophosphonium salts such as [Me,As*PEtJ+Cl- and related compounds have been synthesized.lg3 The reaction between phenylphosphine, PhPH,, and phenylphosphorus dichloride, PhPCl,, which was formerly considered to give the phosphorus analogue of azobenzene, PhP=PPh, is now shown to give a tetrameric product, tetraphenylcyclotetraphosphine (PhP),. The thermal decomposition and chemical reactions of this novel compound are reported.lM Vinyl and tris(trimethylsilylmethy1) derivatives of phosphorus, arsenic, antimony, and bismuth have been prepared and studied.195

A theory of the aromatic character of cyclic phosphoronitrile chlorides (PNCl,), has been developed in which the concept of an aromatic sextet

187 L. Kolditz and A. Feltz, 2. anorg. Chem., 1957, 293, 286; see also L. Kolditz and

188 M. Becke-Goehring and J. Schulze, Chem. Ber., 1958, 91, 1188. 189 G. S. Harris, J., 1958, 512. 190 R. R. Holmes and E. F. Bertaut, J . Amer. Chem. SOL, 1958, 80, 2980, 2983. 191 P. C. Crofts, Quart. Rev., 1958, 12, 34. 192 J. C. Sheldon and S. Y . Tyree, J . Amer. Chem. SOC., 1958, 80, 2117. 19s G. E. Coates and J. G. Livingstone, Chem. and Ind., 1958, 1366. 194 W. Kuchen and H. Buchwald, Chem. Ber., 1958, 91, 2296. 196 L. Maier, D. Seyferth, F. G. A. Stone, and E. G. Rochow, J . Amer. Chem. SOL,

D. Hass, ibid., 1958, 294, 191.

1957, 79, 5884; D. Seyferth, ibid., 1958, 80, 1336.

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of electrons is merely incidental; both the trimeric and tetrameric rings (containing 6 and 8 electrons, respectively) are aromatic, in contrast to benzene and cyclo-octatetrene for which only the six-membered ring is aromatic.lg6 The X-ray single-crystal structure of (PNCl,), confirms the presence of a planar six-membered ring of alternate phosphorus and nitrogen atoms, with two chlorine atoms attached to each phosphorus atom in a plane perpendicular to the ring.lg7 Three new mixed phosphoronitrile halides have been prepared by the reaction of bromine-containing phosphorus halides with ammonium chloride or bromide. They are P,N,Cl,Br, m. p. 123", P,N,Cl,Br,, m. p. 135", and P,N,Cl,Br,, m. p. 169".lg8 Trimeric phosphoronitrile chloride and hydrazine in ether afford the white, crystalline hexahydrazide P3N3(N,H3)6.199 The chlorine atoms can also be replaced by isothiocyanate groups; thus reaction with potassium thiocyanate in acetone200 gives P,N,(NCS),, m. p. 42". Reaction of the trimer with phosphorus pentachloride yields a new compound P,NCl, which was also obtained by direct addition of phosphorus trichloride to N,S,. The suggested structure is PCl,+PNCl,- and it is noteworthy that, since N- is isoelectronic with 0 and C1+, the new anion PNC1,- is isoelectronic with the known 201 species POCl, and PC1,+.201

Arsenic, antimony, and bismuth. The confusion regarding the formulation of alkali-metal arsenites has been resolved. Sodium arsenite is NaAsO,, not Na,HAsO,, and a single-crystal X-ray analysis shows that each arsenic atom is at the apex of a triangular pyramid having three oxygen atoms as a base, the AsO, units being linked in chains by shared oxygen atoms (19). The compound is therefore correctly called sodium polymeta- arsenite and is structurally related to the monoclinic form of arsenious oxide (20) which is also polymeric.202 The structure of arsenious acid in aqueous

solution between pH 2 and pH 14 has been investigated by ultraviolet spectroscopy, diffusion, cryoscopy, potentiometric and conductimetric titration, and paper chromatography. It is concluded that there is an equilibrium between monomeric HAsO, and small amounts of H,AsO, which is independent of the type of arsenious oxide or arsenite disso1ved.m The first well-defined oxyhalide of arsenic has been reported; arsenyl fluoride, AsOF,, was made by direct fluorination of an equimolar mixture

196 D. P. Craig and N. L. Paddock, Nature, 1958, 181, 1052; see also M. Becke- Goehring and K. John, Angew. Chem., 1958,70, 657, for reactions.

197 A. Wilson and D. F. Carroll, Chem. arzd Ind., 1958, 1558. 198 R. G. Rice, L. W. Daasch, J . R. Holden, and E. J. Kohn, J. Inorg. Nuclear Chem.,

198 R. J . A. Otto and L. F. Audrieth, J. Amer. Chem. Soc., 1958, 80, 3575. 200 Idem, ibid., p. 5894. 201 W. L. Groeneveld, J . H. Visser, and A. M. J. H. Seuter, J. Inorg. Nuclear Chem.,

2Oe J . W. Menary, Acta Cryst., 1958, 11, 742. 20s G. Jander and H. Hofmann, 2. anorg. Chem., 1958, 296, 134.

1958, 5, 190.

1958, 8, 245.

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ADDISOX AND GREENWOOD: XIAIS GROUPS. 135

of arsenious oxide and arsenic trichloride; it melts a t -68.3", boils a t -25.6", is readily hydrolysed, and its constitution was confirmed by analysis, molecular weight, mass spectrum, and infrared spectrum.204

The chemistry of fluoroarsenates, hydroxyfluoroarsenates , and hydroxy- fluoroantimonates has been extensively studied,205 and several complexes containing the cation AsCl,+ have been synthesized, e.g., AsCl,+MCl,-, where M = Al, Ga, Fe, A u . ~ ~ The addition compounds of arsenic trichloride and tribromide with copper and silver which are described in the older literature have been shown by X-ray diffraction to be mixtures of CU(I) or Ag(1) halides with amorphous arsenic.207

A nuclear magnetic resonance study of liquid antimony pentafluoride indicates three non-equivalent sets of fluorine atoms in the ratio 1 : 2 : 2. A model which explains the spectra and also interprets the extraordinarily high viscosity of the liquid envisages the compound as a mixture of long chains of SbF, groups, each sharing two fluorine atoms with two neighbours. The three types of fluorine atoms are then (a) bridging fluorine atoms, (b) fluorine atoms trans to these, and (c) non-bridging fluorine atoms trans to each other. At 80" only a single broad line is obtained in the spectrum, the loss of detail being due to rapid fluorine-atom exchange.2o8 The use of antimony trichloride 209 and antimony tribromide as ionizing solvents has been extended.

Literature on the lower halides of bismuth was reviewed and the preparation and properties of the monochloride BiCl were studied in some detail. It is a black, diamagnetic solid formed by reaction of the trichloride with bismuth below 323". Cryoscopic and vapour-pressure data have been interpreted in terms of a cyclic tetramer Bi,Cl,. The compound is stable in air a t room temperature but disproportionates into bismuth and the trichloride above 323". With aluminium chloride it gives the previously reported BiAlCl,. There is no evidence for a dichloride.,ll

Group VI.-It is claimed that a 67% yield of the peroxide H,O, is obtained by bombarding a film of pure ozone with atomic hydrogen a t - 196°.212 Proton resonance spectra indicate that alkali metal perborates are true peroxy-salts with water of crystallization. On the other hand, the so-called perpyrophosphates and percarbonates of sodium contained hydrogen peroxide of crystallization ; the pyrophosphates should therefore be formulated as Na,P,O,,nH,O, rather than Na4P,08,nH20 and the structure Na2C0,,2H,O is probably also incorrect, the spectrum being consistent with the more normal formulation 2Na2CO3,3H20,.2f3

z04 G. Mitra, J . Amer. Chem. SOC., 1958, 80, 5639. 205 L. Kolditz and D. Sarrach, 2. anorg. Chem., 1957, 293, 132; L. Kolditz and

2O6 L. Kolditz and W. Schmidt, 2. anorg. Chem., 1958, 296, 188. 207 W. Rudorff and J. Gelinek, Chem. Ber., 1957, 90, 2654. 208 C. J. Hoffman, B. E. Holder, and W. L. Jolly, J . Phys. Chew., 1958, 62, 364. 209 G. B. Porter and E. C. Baughan, J., 1958, 744. 21* G. Jander and J. Weis, 2. Elektrochem., 1957, 61, 1275; 1958, 62, 850. e l l J. D. Corbett, J . Amer. Chem. SOC., 1958, 80, 4757; J . Phys. Chem., 1958, 62,

212 N. I. Kobozev, I. I. Skorokhodov, L. I. Nekrasov, and Y e . I. Makarova, Zhur.

219 T. M. Connor and R. E. Richards, J., 1957, 289.

W. Rohnsch, ibid., p. 168.

1149.

fiz. Khim., 1957, 31, 1843.

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Recent work 011 the inorganic chemistry of sulphur was the subject of a Chemical Society Symposium.214 A contribution to the optical crystallography of the various allotropes of sulphur has been published.215

The first direct synthesis of the pure sulphanes H2S, and H2S4 has been achieved by reaction of the appropriate chlorosulphane S,C12 with excess of liquid hydrogen sulphide. The viscosities of the sulphanes from H2S2 to H2S, when expressed as log r) increase linearly with chain length, and the activation energy increases concurrently. The heats of formation and evaporation, the critical temperatures, and other physical properties of these compounds are also reported.216 Further methods have been devised for the synthesis of chloro-, bromo-, and cyano-sulphanes Sax2 (n = 1-8) 217

and the preparation of bisdialkylaminosulphanes is described : R2N*S;NR2, where R = Me, Et ; n = 2,3, 4.218

The chemistry of the sulphur nitrides and their derivatives has been re~iewed.2~~ From the relation between S-S bond length and bond order in a variety of compounds it is concluded that the S-S distance of 2.58 A in tetrasulphur tetranitride implies pure $-bonding (21) .220 An analogous but inverse structure has been suggested for realgar, As,S,, in which the As-As distance is 2.47 A. Normally, oxidizing agents convert tetrasulphur tetraimide into the tetrasulphide but when the former is heated in air at

120°, especially in the presence of powdered sulphur, tetrathionyl tetraimide, (OSNH), (22), is obtained as an orange-red solid.221 An improved preparation of the imide S,NH is described which involves the reaction of ammonia with sulphur dichloride in dimethylformamide at Oo.222 Reaction of the imides S7NH and S,(NH), with triphenylmethylsodium gave the sodium derivatives Na[NS,] and NaJNS], which are more unstable and reactive than the imides themselves. Treatment of the tetranitride with ammonia gave the imide-amide HN=S=N*S*NH, which afforded the brown sodio- derivative Na[--N=S=N*S*NH,] and the yellow, explosive trisodio-derivative

214 Chem. SOC. Special Publ., 1958, No. 12, 247. 21s 0. Erametsa, Suomen Kern., 1958, 31, B , 237, 241, 246; see also G. Gee, ref.

214, p. 247, and N. H. Hartshorne, ref. 214, p. 253. 216 F. FCher and W. Kruse, 2. anorg. Chem., 1958, 293, 302; F. FCher, W. Kruse,

and W. Laue, ibid., 1957, 292, 203; F. FCher and G. Winkhaus, ibid., p. 210; F. FCher and G. Hitzemann, ibid., 1958, 294, 50.

F. F6her and S. RistiE, ibid., 1958, 293, 307, 311; F. FCher and H. Weber, Chem. Ber., 1958, 91, 642; see also F. FCher, ref. 214, p. 305.

M. Becke-Goehring, ref. 214, p. 45; H. Garcia-Fernandez, Bull. SOC. chim. France, 218 H. Jenne and M. Becke-Goehring, Chem. Ber., 1958, 91, 1950.

220 I. Lindqvist, J . Inorg. Nuclear Chem., 1958, 6, 159. 221 E. Fluck and M. Becke-Goehring, 2. anorg. Chem., 1957, 292, 229. 222 M. Becke-Goehring, H. Jenne, and E. Fluck, Chem. Ber., 1958, 91, 1947.

1958, 265.

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ADDISON AXD GREENWOOD : MAIK GROIJPS. 137

Na.J-N=S=N*S-N=] .,23 Boron trifluoride is absorbed at room temperature by solid tetrasulphur tetranitride to form the carmine-red adduct BF3,4S,N, which sublimes at 95" in an atmosphere of boron trifluoride. The structures of this compound and the green complex BF3,S4N4F, are being studied by X-ray diffraction.,=

The system SO,-D,O has been investigated and the m. p. of D,SO, found to be 14.35" (cf. 10.37' for H,S04). Cryoscopic and conductivity measurements indicate that the extent of self-dissociation is less in the deutero-compound and that dideuterodisulphuric acid, D,S,O,, is a weaker acid in D,S04 than is H,S,O, in H,S0,.225 Work mentioned in last year's Report (p. 116) on the oxyacids of sulphur has been extended226 and the whole subject reviewed.,,' The solvate of barium pentathionate with acetone, BaS(S,O,),,Me,CO,H,O, has the same internal structure as the dihydrate, one water molecule being replaced by acetone. The middle S-S bonds of the pentathionate ion (23) are 4% shorter than the outermost S-S bonds and contain some double-bond character.,,* The telluropentathionate ion, Te(S,0,),2-, has the same structure.,% The configuration of the sulphur

2-

chain in the hexathionate ion in K,Ba(S,O,), is &cis (24) as in the pentathionate ion (23) and the S, ring of orthorhombic sulphur. (The trans-trans- chain, such as occurs in the helical chains of fibrous sulphur, is known in czesium hexa~ulphide .~~~) The reactivities of penta- and hexa-thionates with nucleophilic reagents have been reviewed. Normally, cleavage involves the formation of thiosulphate but other modes lead to the formation of sulphate and of thiosulphate and sulphur.230

The chemistry of compounds containing sulphur and fluorine has been reviewed.231 Sulphamyl fluoride, H,N*SO,F, m. p. 8O, was made by fluorination of the chloride with potassium fluoride in acetonitrile; it reacts explosively with water to give sulphamic and hydrofluoric Sulphuryl

223 M. Becke-Goehring and R. Schwarz, 2. anorg. Chem., 1958, 296, 3; see also 0. Westphal, H. H. Brauchle, and H. Hurni, Pharm. Acfa HeZv., 1958, 33, 429.

224 0. Glemser and H. Ludemann, Angew. Chem., 1958, 70, 190. 225 R. H. Flower. R. J. Gillespie, J. V. Oubridge, and C. Solomons, J., 1958, 667;

see also B. J. Kirkbride and P. A. H. Wyatt, ibid., p. 2100; Trans. Faraday SOC., 1958, 54, 483.

226 M. Schmidt and G. Talsky, Angew. Chem., 1958, 80, 312; M. Schmidt, B. Wir- woll, and E. Fliege, ibid., p. 506; M. Schmidt and R. R. Wagerle, ibid., pp. 572, 572, 594; F. FCher, J. Schotten, and B. Thomas, 2. Naturforsch., 1958,13b, 624.

227 F. H. Pollard and D. J. Jones, ref. 214, p. 363. 228 0. Foss and 0. Tjomsland, Acta Chem. Scand., 1958, 12, 44, 52. 229 0. Foss, A. Hardvik, and K. H. Palmork, ibid., p. 1339. 230 0. Foss, ibid., p. 959; see also V. A. Lunenok-Burmakina, Zhur. obshchei Khim.,

231 R. N. Haszeldine. ref. 214, p. 317. 232 R. Appel and W. Senkpiel, Angew. Chem., 1958, 70, 572.

1957, 27, 311, for studies with radioactive sulphur.

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138 I N ORGANIC CHEMISTRY.

di-isocyanate, O,S(NCO),, m. p. -4", b. p. 139", and disulphuryl di-isocyanate, S,O,(NCO),, m. p. 26", have also been prepared.= Alkali-metal azides when warmed with excess of sulphur trioxide give as one of the products disulphuryl diazide, S205(N3),, m. p. 7", which hydrolyses slowly in dilute alkali to SO,N,-, SOZ-, and N,-.234 The reaction between thionyl chloride and ammonia usually gives the volatile, colourless, thionyl imide, OS=NH, which polymerizes a t higher temperatures to a yellow or brown solid. However, when the reaction is carried out in chloroform in which calcium oxide is suspended, a deep red isomer is obtained: OSCl, + NH, + CaO - CaCl, + H,O + HOSN. With excess of thionyl chloride, tris- (thiazyl chloride), (NSCl),, is obtained and with excess of ammonia, the reaction affords imidodisulphinamide HN (SO*NH,),. The red hydroxyl isomer can be metallated with triphenylsodiomethane to give NaOSN, which is much more stable than the hydrogen c o m p o ~ n d . ~ ~ The orange-red tetramer (22) was mentioned on p. 136.

Thionyl chloride is a useful reagent for preparing anhydrous inorganic chlorides from their hydrat es.236

The addition compound SeO,,C,H,N was prepared by direct reaction of selenium trioxide with pyridine; it reacts with liquid ammonia to give ammonium amidoselenate, NH,(SeO,*NH,), and also ammonium selenate and selenite.237 Selenium trioxide gives potassium diselenate when heated with potassium chloride: 3Se0, + 2KC1 _t K,Se,O, + SeO, + Cl,. Potassium bromide gives the ele en ate.,,^ The previously unknown SeO,F, was prepared in good yield by warming barium selenate with excess of fluorosulphuric acid at 50": BaSeO, + 2HS0,F __t SeO,F, + Ba(HSO,),. The compound melts at -99.5", boils a t -8*4", is hydrolysed to selenic and hydrofluoric acids, and is more reactive than SO,F,. Its physical properties are also reported.239 A number of ammonia and amine complexes of selenium and tellurium tetrachlorides have been prepared and characterized, and their stabilities investigated by differential thermal analysis.240

Trifluoromethyl derivatives of selenium have been investigated in some detail. The reaction between trifluoromethyl iodide and selenium at 260-280" yields the selenide, (CF,),Se, b. p. -2", and the diselenide, (CF,),Se,, b. p. 73", in a ratio of about 4 : 1. The diselenide decomposes to the monoselenide and selenium in ultraviolet light. Chlorination of both compounds under appropriate conditions gives CF,*SeCl or CF,*SeCl,. Bromine reacts similarly. Nitric acid oxidation of the diselenide or hydrolysis of the trichloride affords trifluoromethylseleninic acid, CF,*SeO,H, m. p. 119". The diselenide and the monochloride both give bistrifluoro- methylmercury with mercury and this compound reacts with anhydrous hydrogen chloride to give CF,*SeH, b. p. -14.5". It appears that the

2.38 R. Appel and H. Gerber, Chem. Ber., 1958, 91, 1200; Angew. Chem., 1958, 70 271.

234 H. A. Lehmann and W. Holznagel, 2. anorg. Chem., 1958, 293, 314. 235 M. Becke-Goehring, R. Schwarz, and W. Spiess, ibid., p. 294. 236 J. H. Freeman and M. L. Smith, J. Inorg. Nuclear Chem., 1958, 7 , 224, 287. 237 K. DostAl and K. KrejEi, Z . anorg. Chem., 1958, 296, 29. 238 J. FrkQii, Chem. Zvesti, 1958, 12, 330. 239 A. Engelbrecht and B. Stoll, 2. anorg. Chem., 1957, 292, 20. 240 V. G. Tronev and A. H. Grigorovich, Zhur. neorg. Khim., 1957, 2, 2400.

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ADDISOK AND GREENWOOD: MAIN GROUPS. 130

trifluoromethyl derivatives of selenium are more reactive than the analogous sulphur compounds owing to the relative weakness of the C-Se and Se-Se bonds. The ability to form quadrivalent selenium compounds involving halogens (not readily formed by the sulphur analogues) and the formation of CF,*SeO,H as the most stable acid (in contrast to the sulphonic acid CF,*SO,H) are also trends which accord with the general chemistry of selenium and sulphur.=l

Thiourea forms four types of complex with tellurium tetrahalides (X = C1, Br), the products depending on the solvent used and the relative concentration of the reactants; the compounds are (CSN,H,),TeX,, (CSN,HJ2TeX,, (CSN,H,),TeX6,2CSN,H,X, and disubstitution products of the form (CSN2H,),TeX,.242

New methods of preparing polonium metal have been developed. Liquid ammonia reduces the hydroxide Po(OH), and other compounds, and alkaline reduction can also be effected by hydrazine, hydroxylamine, or sodium dithionite; PoCl, is reduced in hydrochloric acid solution by stannous chloride, titanium trichloride, or dithionite.2a Polonium tetra- nitrate, which was prepared by the action of dinitrogen tetroxide on PoO, or PoCl,, slowly decomposes in air at room temperature to give a basic salt; this, in turn, decomposes at higher temperatures to give a second basic salt. Both compounds appear to have dimeric or polymeric oxygen-bridged structures and possible formulations are discussed. Evidence for a polonium nitrite is also presented.M Partition of molar polonium(1v) between aqueous acids and isobutyl methyl ketone has been studied. Addition of strong oxidants such as Ce4+ or Cr0,2- displaces the equilibrium towards the aqueous phase but addition of hydrogen peroxide re-establishes the original equilibrium. The effect confirms the existence of polonium(vI), the potential of the couple polonium(1v)-(vI) being about 1-5 v.245 The volatility of polonium compounds extractable with organic solvents in the presence of organic complexing reagents is greater than the volatility of species extracted in the absence of such reagents.246

Group VI1.-The physical and chemical properties of the halogen fluorides and other covalent fluorides have been reviewed.247 Values for surface tension and viscosity of bromine trifluoride and pentafluoride and of iodine pentafluoride over a range of temperature are reported. These, in con- junction with published data on chlorine trifluoride and the energies of vaporization, suggest that chlorine trifluoride and bromine pentafluoride are probably normal liquids whilst bromine trifluoride and iodine pentafluoride are associated.w Raman and infrared spectra of chlorine and bromine trifluorides confirm the planar T-shaped structure of these molecules and lead to values of their thennodynamic properties between 250" and 1000" ~ . 2 4 9

241 J. W. Dale, H. J. EmelBus, and R. N. Haszeldine, J., 1958, 2939. 242 E. E. Aynsley and W. A. Campbell, J. , 1958, 3290. 24s K. W. Bagnall, P. S. Robinson, and M. A. A. Stewart, J., 1958, 3426. 244 K. W. Bagnall, D. S. Robertson, and M. A. A. Stewart, J. , 1958, 3633. 245 N. Matsuura and M. Haissinsky, J. Chim. phys., 1958, 55, 475. 246 H. Mabuchi, Bull. Chem. SOC. Japan, 1958, 31, 245. a4' H. C. Clark, Chem. Rev., 1958, 58, 869. 248 M. T. Rogers and E. E. Garver, J. Phys. Chem., 1958, 62, 952. 349 H. H. Claassen, B. Weinstock, and J. G. Malm, J. Chem. Phys., 1958, 28, 286.

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Nitrosonium tetrafluorobromate, NO+BrF4-, has been prepared by direct reaction of nitrosy1 fluoride and bromine trifluoride and by passing nitric oxide through bromine trifluoride: 3N0 + 4BrF3 --+ 3NOBrF, + 4Br2. The bromine trifluoride is readily displaced from the compound to give complexes (NO),MF, where M = Si, Ge, Sn, Ti.250 Experimental details are given for the simple laboratory preparation of iodine pentafluoride in good yield from the pentoxide and either bromine or chlorine trifluoride as the fluorinating agent: 61,05 + 20XF3 _+ 121F5 + 150, + 10X2.251

A systematic study has been made of the changes in the infrared spectrum of the iodine monochloride stretching vibration as the interhalogen forms complexes of increasing stability. The frequency decreases regularly from 375 cm.-l for uncomplexed IC1 in carbon tetrachloride to 275 cm.-l for the strongest complex, ICl,C5H5N. The intensity of the band increases concurrently.252 The formation constants of 1 : 1 complexes of acetonitrile with iodine monochloride, iodine monobromide and iodine have been determined spectroscopically, and the slow increase in electrical conductivity of the acetonitrile solutions of these complexes is attributed to a slow ionization process.= The voltametric behaviour of the solutions is also reported.254 Potassium dichloroiodide has been prepared by wet and by dry methods and analytical deficiencies in the product obtained by the wet method have been shown to be due to the formation of the hydrate, KIC1,,H20, despite previous (inconclusive) arguments that this hydrate did not exist. The dissociation pressure of this monohydrate agrees with earlier values on material thought to be anhydrous and the true anhydrous compound has, in fact, a much lower dissociation pressure. Powder photographs are also recorded.255

An X-ray single-crystal analysis of the complex Br2,C6H6, m. p. -14", indicates a structure comprising straight chains of alternating benzene and bromine molecules, the benzene rings being parallel to each other and perpendicular to the chains, whilst the bromine molecules lie along the chains perpendicular to the benzene rings and on their common principal axis. It appears that the x-electrons of all six carbon atoms are involved equally in the bonding.256 The 1 : 1 complex of bromine with acetone also has infinite chains, both non-bonding pairs of electrons on the oxygen atom being involved (25). The keto-carbon, oxygen, and bromine atoms are coplanar and the methyl groups slightly out of the plane. The Br-Br bond distance in this complex and the benzene complex is 2.28 A, very close to the value in free bromine itself .257

The infrared absorption of hydrogen fluoride vapour between -70" and +73" is strongly dependent on pressure and temperature. In special

250 A. Chrdtien and P. Bouy, Compt. rend., 1958, 246, 2493. 251 G. A. Olah, A. E. Pavlath, and S. J. Kuhn, J . Inorg. Nuclear Chem., 1958, 7,

301. 252 w. B. Person, R. D. Humphrey, W. A. Deskin, and A. I. Popov, J . Amer. Chent.

sot., 1958, 80, 2049; see also S. Nagakura, ibid., p. 520. 253 A. I. Popov and W. A. Deskin, ibid., p. 2976. 254 A. I. Popov and D. H. Geske, ibid., p. 5346. 255 G. F. Allison and G. H. Cheesman, J. , 1958, 1177. 256 0. Hassel and K. 0. Strarmme, Acla Chem. S c ~ n d . , 1958, 12, 1146. 257 Idem, Nature, 1958, 182, 1155.

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circumstances absorption varies either as the 4th or the 6th power of the pressure but normally the absorption corresponds to the overlapping spectra of the tetramer and hexamer. Heats of polymerization are estimated to be 19 and 40 kcal. mole-l, respectively. Deuterium fluoride behaves similarly.2m An infrared study of hydrogen bonding and molecular- complex formation has been carried out on solutions of anhydrous hydrogen

I\

Me/"Me ;

(25) Me' 'Me

fluoride (and sometimes deuterium fluoride) in a selection of ten represent- ative organic s0lvents.25~ Tetramethylammonium hydrogen dichloride , Me,N+HCl,-, has been prepared, its X-ray powder photograph indexed, and the infrared spectrum of the HC1,- ion shown to be similar to that of the more familiar HF,- ion.260

The reaction of ammonium fluoride with metal bromides in methanol has been established as a general method for synthesizing ammonium fluorometallates. Typical examples of the 17 complexes prepared are NH,MnF,, NH,BiF,, (NH,),TiF,, and (NH,)31nF6.261 Fluorine nitrate, N03F, decomposes explosively into NOF and oxygen when sparked, but the slow first-order thermal decomposition can be studied kinetically a t temperatures between 80" and 110°.262

Viscosity and specific gravity isotherms of aqueous solutions of perchloric acid establish the following hydrates: 1, 2, 2*, 3, and 3$.263 The exo- thermic reaction between dichlorine hexaoxide and fluorine yields 70-75y0 of C102F, 20-%y0 of Cl,O,, 1-3y0 of Cl,, and small amounts of a more volatile product C10,F. The mechanism of the reaction is discussed.264 Further methods for preparing chloryl fluoride, ClO,F, have been developed; these involve the fluorination of chlorine dioxide with argentic fluoride or bromine trifluoride and the reaction of dichlorine hexaoxide with nitryl fluoride. Improved syntheses of bromyl fluoride are also reported. These use bromine pentafluoride to fluorinate bromine dioxide, potassium bromate, or a mixture of bromine and ozone. The compound melts a t -9"

258 D. F. Smith, J . Chem. Phys., 1958,28, 1040; see also P. A. Giguhre and N. Zengin,

259 R. M. Adams and J. J. Katz, J . Mol. Spectroscopy, 1957, 1, 306; see also M. L.

260 T. C. Waddington, J. , 1958, 1708. 261 H. M. Haendler, F. A. Johnson, and D. S. Crocket, J . Amer. Chem. SOC., 1958,

262 W. E. Skiens and G. H. Cady, ibid., p. 5640. 263 A. A. Zinov'yev and V. P. Babayeva, Zhuv. neorg. Khim. , 1957, 2, 2188. 264 IV. H. Basualdo DQvila, Rev. Fac. Cienc. qztinz., Univ . jzac. L a Plata, 1957, 29, 27.

Canad. J . Chem., 1958, 36, 1013, for spectrum of solid.

Josien, P. Grange, and J. Lascombe, Compt. rend., 1958, 246, 3339.

80, 2662.

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and decomposes at 56” according to the equation 3Br02F + BrF, + Br2 + 302.265

3. THE TRANSITION ELEMENTS

MUCH of the work published during the year on the chemistry of the transition elements has again been concerned with the chemistry of complexes. Those aspects which illustrate the general properties of complexes or ligands, and which are not necessarily characteristic of any single transition metal, are discussed first under the heading “ complexes ”. The chemistry of the elements is then discussed systematically in the ten transition groups.

The proceedings of the International Symposium on Co-ordination Compounds, held in Rome in September 1957, have now been published.266 The field was fully reviewed, and the various section headings are given below, with the titles of introductory lectures to each section. 1. The chemical bond : ultraviolet, infrared and Raman spectroscopy; introductory lectures on “ theory of bonding in metal complexes,” 267 “ vibrational spectra and structure of co-ordination compounds,” 268 and ‘ I absorption spectra of complexes in the visible and ultraviolet range.” 269 2. Stereochemistry, reactivity, and stability constants; introductory lectures on “ some problems in the stereochemistry of co-ordination compounds,” 270 “ stability constants,” 271 and “ polarography of metal complexes.” 272 3. Magnetic and structural properties, with introductory lectures on “ magneto- chemistry,” 273 “ nuclear magnetic resonance,” 274 and “ paramagnetic resonance.” 275 4. Valency stabilization and unusual compounds, with introductory lectures on “ the stabilization of low-valency states of the transition metals,” 276 “ stabilization of high valency states,” 277 and “ unusual types of co-ordination compounds.” 278 5. Catalytically active complexes, with an introductory lecture on “ stereospecific polymerizations by means of co-ordinated anionic catalysis.” 279 Complex formation is discussed in a review on “ aqueous metal salt solutions.” 280 The proceedings of a symposium on non-stoicheiometric compounds have been published,B1 and a paper on the ‘‘ chalcogenides of transition elements ” is also concerned with non-stoicheiometry.282

265 M. Schmeisser and W. Fink, Angew. Chew., 1957, 69, 780; M. Schmeisser and

266 J . Inorg. Nuclear Chem., 1958, 8. 267 L. E. Sutton, ibid. , p. 23. 268 J . P. Mathieu, ibid., p. 33. 26s H. Hartmann, ibid., p. 64. 270 J . C. Bailar, ibid. , p. 165. 2 7 1 L. G. SillCn, ibid., p. 176. 272 G. Sartori, ibid., p. 196. 273 R. S. Nyholm, ibid., p. 401. 274 R. E. Richards, ibid., p. 423. 276 J. Owen, ibid., p. 430. 276 J . Chatt, ibid.. p. 515. 277 W. Klemm, ibid. , p. 532. 278 H. M. Powell, ibid., p. 546. 279 G. Natta, ibid.. p. 589. 280 G. Schwarzenbach, Angew. Chem., 1958, 70, 451. 281 Trans. Brit. Ceram. SOC., 1957, 58, 553. 282 H. Haraldsen, X V I Infernat. Congr. Pure Appl. Chem., Experientia Szifipl. V I I ,

1957, 165.

E. Pammer, ibid., p. 781.

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ADDISON AND GREENWOOD : THE TRANSITION ELEMENTS. 143

An attractive theory for polymerization of metal alkoxide polymers has been developed. These polymers are normally small, and much data can be correlated by assuming that the metal alkoxide adopts the smallest structural unit consistent with all the metal atoms’ attaining a higher CO-

ordination number.283 Methods for the preparation of trialkylsiloxy- derivatives of transition metals involve reaction between the appropriate silanol and the metal alk0xide.m

Complexes.-(a) GeneraZ. Magnetic data on the magnetically dilute complexes of the second and the third transition series have been summarized; much of the data can be explained on the basis of large spin-orbit coupling constants, and the possibility of co-ordination numbers greater than six.285 The significance of various factors which influence the stereochemistry of complex halides of the transition metals has been compared. It is emphasized that when crystal field forces are opposed by others they may be swamped, and the structure may be that determined by bond and lattice interactions.28s Magnetic properties of some binuclear complexes of chromium and iron have been studied. These include the chloro-bridged complex [Cl,FeC13FeC13]3-, the 1 , 10-phenanthroline complex [phen,Fe(OH),FephenJ4+, and corresponding chromium complexes. In the ion [C1,CrC1,CrC13]3-, the metal-metal distance is large, and the magnetic moment 3.82 B.M. Data for this and for the iron compound show that the metal-metal distance in the latter should also be long, which is in contrast to the shortening of the iron-iron distance in the iron ennea~arbonyl.~~’ High pressure on a complex (up to 130,000 atm.) has been shown to influence the ligand field, and thus the splitting of the 3d levels. This is interpreted in terms of change in metal-ligand distance, by reference to Cr, Fe, Ni and Co complexes.m

A second form of the complex [Co(NH,),(NO,),] (for which only the trans-isomer is known) has been isolated. Infrared spectra indicate that it is the c i s - i ~ o m e r . ~ ~ Only one form of the related complex [Co(NH,),(NO,),Br] is known and X-ray analysis shows it to be the trans- isomer, with a nitro-group in the trans-position to the bromine atom.290 cis- and tram-Isomers of [Rh py3Cl,] have also been c h a r a ~ t e r i z e d . ~ ~ ~

Further attention has been given to oxidation-reduction reactions involving the metal ion in complexes, the influence on reaction rates exerted by added ions, and the mechanisms concerned. Spontaneous reaction of the ion [Cr(NH,),C1I2+ in acid solution yields [Cr(NH,)5H20]3+ and C1-, but when the chromous ion is present, CrC12+ and NH4+ are formed; halides probably act as bridge groups for electron transfer.292 The exchange rates

2E3 D. C. Bradley, Nature. 1958, 182, 1211. 284 D. C. Bradley and I. M. Thomas, Chem. and Ind., 1958, 17, 1231. Za5 B. Figgis, J , Inorg. Nuclear Chem., 1958, 8, 476. 2a8 N. S. Gill, R. S. Nyholm, and P. Pauling, Nature, 1958, 183, 168. za7 A. Earnshaw and J . Lewis, ibid.. 1958, 181, 1262. 288 R. W. Parsons and H. G . Drikamer, J. Chem. Phys., 1958, 29, 930.

290 Y. Komiyama, Bull. Chem. SOC., Japan, 1958, 31, 26. 291 J . P. Collman and H. F. Holtzclaw, J. Amer. Chem. Sot., 1958, 80, 2054; see also

292 A. E. Ogard and H. Taube, J. Amer. Chem. SOC., 1958, 80, 1084.

A. K. Majumdar, C. Duval, and J . Lecomte, Compt. rend., 1958, 247, 302.

V. Carassiti and 0. Salvetti, Ann. Chim. (Italy), 1958, 48, 844.

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of Cr2+ with CrX2+ (X = F, C1, Br, NCS, or N3) support this mechanism.293 Isotope exchange between platinum(r1) and platinum(1v) has been studied with the compounds [PtenBr,] and [PtenBr,]. In the solid compound [Pt enBr,] no exchange occurs, so that the platinum(I1) and platinum(1v) complexes of which [Pt enBr,] is composed in the solid retain their identity. In dimethylformamide solution, exchange is strongly catalysed by bromide ions, which may act as bridging atoms.294 The very slow exchange of chloride ion with [Pt en,C1,I2+ is catalysed by the presence of [Pt en,],+; this is explained in terms of the mechanism [Pt en,],+ + C1- +, [Pt en2C1]+, in which case the rate of platinum exchange between the platinum(I1) and platinum(1v) species should equal the rate of chlorine exchange. This has been confirmed for the related reaction

[Pt en2I2+ + [Pt pn2C12]2+ + [Pt e n 2 C t 2 ] 2 + -t [Pt pn2]2+

in which the change was followed by optical rotation difference of (-)- propylenediamine (pn) in the two complexes.295 Other exchanges studied include those between the tetracyanonickelate ion and certain amino-acid complexes of nickel(11) ,296 and between the nickel(I1) and the nickel ethylene- diaminetetra-acetate ions.297 Chromatographic analysis has been used to study the aquation of hexa-, penta-, and tetra-amminechromium(II1) ions in acidic and basic solutions; the monoammine [Cr(NH,) (H20)5]3+ was isolated as a czsium alum. This completes the series [Cr(NH,),l3+-------- [Cr(H,0),]3+.298 Experiments with the %o isotope indicate that the exchange of the cobalt atom between the ions [CO(NH3)6]2+ and [Co(NH,),I3+ is faster in liquid ammonia than in aqueous ammonia. The effect is associated with the unusual nature of the electron in liquid ammonia.299 Photochemical reactions of some cobalt (111) and chromium(II1) complexes have also been examined.3m

Available data on the relative affinities of ligand atoms for acceptor molecules and ions have been reviewed.301 The stability constants for complexes of the silver ion with sulphonated aromatic ethers, sulphides, and selenides illustrate that the ether oxygen has little tendency to co-ordinate, while sulphides and selenides form complexes of moderate stability. The relative affinities of nitrogen, phosphorus, and arsenic compounds as ligands in silver complexes have also been compared.302 The first stability constants of the metanilate, 3-~ulphotriphenylphosphine, and 4-sulphodiphenyl sulphide ions with the cadmium ion are all smaller than for analogues with the silver ion; dative x-bonding from metal to ligand thus falls sharply at the end of the transition series.,”

293 D. L. Ball and E. L. King, J . Amer. Chem. SOC., 1958, 80, 1091. 294 R. E. McCarley, D. S. Martin, and L. T. Cox, J . Inorg. Nuclear Chem., 1958, 7 ,

113. 295 F. Basolo, P. H. Wilks, P. G. Pearson, and R. G. Wilkins, ibid., 1958, 6, 161. 296 R. C. Calkins and N. F. Hall, J . Amer. Chem. Soc., 1958, 80, 5028. 297 C. M. Cook and F. A. Long, ibid., p. 33. 298 E. Jrargensen and J. Bjerrum, Acta Chem. Scand., 1958, 12, 1047. 299 J. J. Grossman and C. S. Garner, J. Chem. Phys., 1958, 28, 268. 300 A. W. Adamson and A. H. Sporer, J . Inorg. Nuclear Chem., 1958, 8, 209. 301 S. Ahrland, J. Chatt, and N. R. Davies, Quart. Rev., 1958, 12, 265. 302 S. Ahrland, J. Chatt, N. R. Davies, and A. A. Williams, J . , 1958, 264, 276. 3O3 Idem, J., 1958, 1403.

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Anhydrous ethylenediamine and propylenediamine react with the more ionic transition-metal chlorides, e.g., VCI,, CrCl,, to give [V en,]Cl,, [V pn3]C1,, and [Cr en3]Cl,, whereas the covalent TiCl,, VCl,, and MoCl, are solvolysed. Ferric chlonde is first reduced to the ferrous state, then forms the outer- orbital complex [Fe en,]C12.304 An asymmetric complex ion can influence the reaction of a racemic attacking ligand by favouring reaction by one enantiomer. This has been illustrated by treating (+)-[Co(EDTA)]- with racemic propylenediamine, when (+ )-propylenediamine reacts more rapidly than the (-)-isomer. Treatment of (&)-[Co(EDTA)]- with (-)-propylenediamine gives partial resolution of the racemic complex ion.305 The metal- thiourea (thi) complexes [Pt(thi),Cl,], [Pt(thi),]Cl,, [Pd(thi),]Cl,, [Zn(thi),Cl,], and [Ni(thi),(SCN),] have sulphur-to-metal bonds. In contrast, urea forms nitrogen-to-metal bonds with platinum(I1) and palladium(II), and oxygen-to- metal bonds with chromium(IIr), iron(m), zinc(II), and copper(I1) .306

Characteristic frequencies in the infrared spectrum of some carbonato- metal complexes have been assigned. Three strong bands are found which are absent from the spectra of ionic carbonates. The results have added interest in view of the similarity in the structures of the carbonate and nitrate i0ns.~0' A survey has also been made of the infrared spectra attributable to the nitro-group in complexes. As with carbonyl and thio- cyanato-groups, this technique is of value in determining whether the nitro- group is in terminal or bridging positions, or whether two groups are cis- or trans- to one another.308

Cobaltous complexes of some amino-acids are known to take up molecular oxygen in a reversible reaction which does not involve change in metal valency. The product from the irreversible oxidation of the cobalt (11) glycylglycine complex is identical with glycylglycine cobalt(m), so that irreversible oxidation does in fact involve change in valency of the Formation constants of iron(I1) and manganese(I1) with tetraethylenepenta-amine have been determined. Attempts to oxygenate these complexes were uns~ccessful.~~0 When hydroxyl ions are added to solutions containing the triethylenetetra-amine- cobalt(I1) ion [Co(trien)12+, the complexes [Co(trien) OH]+ and a polymer [*O*Co(trien)*O*] are formed. The tris-2-arninoethylaminecobalt(II) ion [Co(tren)12+ forms [Co(tren)OH]+ and the dimer [C~,(tren)~(OH),,,]+. Only the latter can decompose hydrogen peroxide.311

Ultraviolet spectra of thirty acetylacetone complexes have been reported, The nuclear magnetic resonance spectra of diamagnetic complexes provide no support for the postulate of benzenoid resonance in the chelate rir1gs.3~2 The

304 G. W. A. Fowies and W. R. McGregor, J. , 1958, 136. 305 S. Kirschner, Yung-Kang Wei, and J. C. Bailar, J . Amer. Chem. SOC., 1957, 79,

306 A. Yamaguchi, R. B. Penland, S. Mizuschima, T. J. Lane, C. Curran, and J. V.

307 B. M. Gatehouse, S. E. Livingstone, and R. S. Nyholm, J. , 1958, 3137. 308 B. M. Gatehouse, J . Inorg. Nudear Chem., 1958, 8, 79. 309 M. T. Beck, Naturwzss., 1958, 45, 162. 310 H. B. Jonassen, A. Schaafsma, and I,. Westerman, J . Phys. Chem., 1958, 62,

311 H. B. Jonassen and G. T. Strickland, J . .4mev. Chem. SOC., 1958, 80, 312. 312 R. H. Holm and F. A . Cottnn, ibid., p. 5658.

This is followed by an irreversible process.

5877.

Quagliano, ibid., 1958, 80, 527.

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infrared frequencies assigned to the bent form of the uranyl group have been observed in uranyl a-diketone complexes.313 There are three crystalline modifications of uranyl acetylacetone monohydrate, as well as crystalline solvates of uranyl acetylacetone with ethanol, dioxan, acetylacetone, and acetophenone. The anhydrous compound is dimeric in benzene solution.314 Partial resolution of acetylacetone-chromium(II1) and -cobalt (111) into optically active fractions has been achieved in a column of ~ - 1 a c t o s e . ~ ~ ~

(b) Carbonyls, nitrosyls, cyanides, and related compounds. A novel synthesis which is of particular value for the less accessible transition metal carbonyls, e.g., Cr(CO),, consists of a reductive carbonylation of an appropriate salt of the metal with triethylaluminium and carbon monoxide. The reaction is conducted at high temperature and pressure, ether being used as solvent.31e Di-isobut ylaluminium hydride has been used in similar reactions.,17 Monosubstitution products of chromium hexacarbonyl, Cr(CO),X, where X=NH, or C,H,N, are prepared by reactions involving the ions [Cr(CO)5]z- and [Cr,(CO),,H]- in liquid ammonia. Mechanisms of these reactions have been discussed.318

By means of molecular-orbital theory it has been possible to reconcile the diamagnetism of iron dodecacarbonyl with the structure

involving three bridging carbonyl groups between the metal atoms; this disposes of one major objection to this structure.319 Further substitution products of iron carbonyls with nitrogen bases have been formulated satisfactorily on the basis of formation of the carbonylferrate anion. The piperidine and pyrollidine substitution products are salts of tetra- nuclear carbonylferrate, e.g., [Fe(C,H,N),] [Fe,(CO),,1. y-picoline gives [Fe(C,H,N),] [Fe,(C0),].320 Products of reaction of dicobalt octacarbonyl with a series of amines and nitriles can be represented in similar fashi0n,3~f and this is supported by infrared spectra.322 Iron carbonyl chalcogenides,

Fe,X,(CO), (X=S, Se, Te), can be prepared by reaction of the [Fe(C0),l2- ion with /\> F~(co) , sulphurous, selenious, or tellurous acid. The compounds are diamagnetic, hydrophobic, and

( co”Fe\ x ’ / (26) relatively stable. Infrared spectra support the structure (26). With a polysulphide, the tetracarbonylferrate ion gives the ruby-red, volatile Fe,S,(CO),, which has a structure analogous to that of the red Roussin salt.323

(CO),Fe(CO),Fe (CO),Fe( CO),

818 L. Sacconi, G. Caroti, and P. Paoletti, J . Inorg. Nuclear Chem., 1958, 8, 93;

814 A. E. Comyns, B. M. Gatehouse, and E. Wait, J., 1958, 4655. 315 T. Moeller and E. Gulyas, J . Inorg. Nuclear Chem., 1958, 5, 245 316 H. E. Podall, J . Amer. Chem. SOC., 1958, 80, 5573. 317 L. I. Zakharkin, V. V. Gavrilenko, and 0. Yu. Okhlobystin, Izvest. Akud. Nauk

318 H. Behrens and W. Klek, 2. anorg. Chem., 1957, 292, 151. 31s D. A. Brown, J . Inorg. Nuclear Chem., 1958, 5, 289. 320 W. Hieber and N. Kahlen, Chem. Ber., 1958, 91, 2223, 2234. 321 W. Hieber and R. Wiesboeck, ibid., pp. 1146, 1156. 322 0. Vohler, ibid., p. 1161. 323 W. Hieber and J. Gruber, 2. aaovg. Chem., 1968, 296, 91.

J., 1958, 4257.

S.S.S.R., Otdel. khim. Nuuk, 1958,, 100.

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ADDISON AND GREENWOOD THE TRANSITION ELEMENTS. 147

Further studies on organomanganese pentacarbonyls R*Mn(CO), have been published. The methyl, ethyl, and n-propyl compounds are prepared by the general reaction Na[Mn(CO),] + RI + R*Mn(CO), + NaI. The benzoyl derivative can also be prepared from bromopentacarbonyl- manganese and benzoylmagnesium chloride.324 The dimeric tetracarbonyl- rhenium halides [Re(CO)4X]2, where X = C1, Br, or I, result from thermal decomposition of corresponding pentacarbonyl halides, into which they may be reconverted by carbon monoxide at high temperature and pressure. The tetracarbonyl iodide gives with pyridine a monomeric compound Re(C,H,N),(CO),I, identical with that obtained by reaction of pyridine with pent acarbon ylrhenium iodide .325

Tetracarbonylmethylcobalt MeCo(CO), is analogous to the manganese compound MeMn(CO),, but is only stable at low temperatures. It is prepared by a similar method.326 A molecular-orbital treatment of the binding of the hydrogen atom in cobalt carbonyl hydride indicates that Co-H bonding is important; the hydrogen atom lies within 1.2 A of the cobalt atom, and is thus buried in the electrical density of the metal atom.,,' When rhodium(1) complexes RhL,(CO)Cl (L = Ar,P, Ar,As, Ar3Sb) in chloroform are treated with a halogen, octahedral complexes of rhodium(m), RhL,(CO)X, (where X = C1, I), are obtained. These are monomeric, diamagnetic non-electrolytes. They have high thermal and chemical stability; even the stibine complexes are not decomposed by boiling concentrated hydrochloric acid or cold alcoholic alkali.328 Carbonyliridium halides Ir(CO),X and Ir(C0)2X, are known ; complexes involving other ratios have now been formed from carbon monoxide and potassium hexahalogenoiridates a t high pressure. From K21rC16, the products K [Ir (CO),Cl,.,] , K [Ir (CO) ,Br2.,], K [Ir(CO) Br,] , and K [Ir (CO),Br,] have been isolated. They are probably d i m e r i ~ . ~ ~ ~

The Raman spectrum of liquid Ni(PF,), supports a regular tetrahedral structure. The force constant for stretching of the Ni-P bonds (2.71 x 105 dynes/cm.) is considered to be remarkably low in view of other evidence that the bonds have appreciable double-bond character.=O Nickel carbonyl reacts with excess of tristrifluoromethylphosphine at room temperature to form a mixture of the substitution products (CF,),P,Ni(CO), and [(CF,),P],Ni(CO),; high temperature favours the latter.=l It has not yet been possible to prepare the fully-substituted [(CF,),P],Ni. In fact, the disubstituted product fails to react with excess of (CF,),P at 100". With the diphosphine P2(CF3),, nickel carbonyl gives a product (CO),Ni-P (CF,) , n P (CF,) ,*Ni (CO) ,, and the c y clo t e t raphos phine ( CF,P) also gives substitution products not yet ~haracterized.,~, In view of the reluctance of diarsine to form the complex Ni[o-C,H,(AsMe,),],, it is of

324 W. Hieber and G. Wagner, Annalen, 1958, 818, 24. 325 E. W. Abel, G. B. Hargreaves, and G. Wilkinson, J. , 1958, 3149. 326 W. Hieber, 0. Vohler, and G. Braun, 2. Naturforsch., 1958, 13b, 192. 327 F. A. Cotton, J . Amer. Chem. SOC., 1958, 80, 4425. 328 L. Vallarino, J . Inorg. Nucleav Chem., 1958, 8, 288. 329 L. Malatesta and M. Angoletta, ibid., p. 273. 330 L. A. Woodward and J. R. Hall, Nature, 1958, 181, 831. 331 H. J. Emel6us and J. D. Smith, J., 1958, 527. 332 A. B. Burg and W. RIahler, J . A n w . Ckenz. SOC., 1958, 80, 2334,

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interest that the diphosphine o-C,H,(PEt,), forms a nickel(0) complex more readily. The monochelate complex [o-C,H,(PEt,),]Ni(Co), is treated with the diphosphine at 150", and the nickel(0) compound [o-C6H4(PEt,),],Ni is obtained as red crystals, m. p. 241-243'. This can also be prepared by direct solution of finely divided nickel in the ligand at 160°.333 Platinum forms zerovalent compounds with triarylphosphines, triarylarsines, and triaryl phosphites more readily than does palladium. The compound Pt (PPh,), will disproportionate to give the co-ordinatively unsaturated Pt(PPh,),, and in common with other phosphine derivatives, reacts with carbon monoxide to give mixed carbonyl-phosphine compounds, e.g.,

The mechanism whereby molecular hydrogen is evolved from aqueous cobaltous cyanide-potassium cyanide solutions has presented a problem for many years. The kinetics of hydrogen evolution have recently been studied. Addition of alkali metal ions increases the rate, which is also pH- dependent.= Considerable progress towards a solution of the problem has been made by the observation that in these solutions a proton resonance occurs at a position characteristic for a proton bound to a metal atom. The proton is derived from water, since an atmosphere of hydrogen is not necessary for appearance of the resonance line, which also disappears on introduction of oxidizing agents. The ion [HCo(CN),I2- is postulated as the hydrogenated species.336 Re-examination of the infrared spectra of the cyanides K4[Ni(CN),l2 and K,[Co(CN),], suggests that they contain metal- metal bonds. The structure of the cobalt complex ion is then analogous to that for Re2(C0)10.337 The infrared spectrum of the ion [Ni(CN),]4-, which is isoelectronic with nickel carbonyl, shows one main band at 1985 cm.? consistent with a tetrahedral structure.=

The strongly covalent metal-nitrate ion bonding first observed in anhydrous cupric nitrate exists in a similar ferric compound also. Ferric chloride reacts with a dinitrogen tetroxide-ethyl acetate mixture, yielding pale brown crystals of empirical formula Fe(NO,),,N,O,. This compound can be sublimed in a vacuum at 120". Infrared spectra and magnetic susceptibility support a structure NO+[Fe(N0,)4]- for the solid; in the vapour a pentaco-ordinated complex Fe(N0) (NO,), seems probable, which has analogies with iron p e n t a c a r b o n ~ l . ~ ~ Measurement and classification of the infrared spectra of over 50 metal-nitric oxide complexes is a valuable contribution to structural studies in this fieldsM0 In most complexes bonding occurs by donation of two electrons from the nitric oxide group, together with coupling of the unpaired electron with an unpaired d-electron of the metal to give a x-bond. There are examples in which nitric oxide can bond in a manner resembling metal-olefin complexes. The N-O stretching

333 J. Chatt and F. A. Hart, Chem. and Ind., 1958, 1474. 333 L. Malatesta and C. Cariello, J . Inorg. Nuclear Chem., 1958, 8, 561; J. , 1958,

335 N. K. King and M. E. Winfield, J . Amer. Chem. SOC. , 1968, 80, 2060. 336 \v. p. Griffith, L. Pratt , and G. Wilkinson, Nature, 1958, 182, 466. 337 W. P. Griffith and G. Wilkinson, J . Inorg. Nuclear Chem., 1958, 7 , 295. 3313 M. I;. Amr El Sayed and R. K. Sheline, J . .4mer. Chem. SOC., 1958, 80, 2047. 339 C. C. Addison, B. J. Hathaway, and N. Logan, Proc. Chem. SOC., 1958, 51. 340 J. Lewis, R. J . Irving, and G. Wilkinson, J . Irzorg. Nicclear Chem., 1958, 7, 33.

Pt(C0)2(PR3)2'334

2323.

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frequencies lie in the range from -1940 cm.-l to 1045 cm.-l, compared with the narrower range from -2100 to 1850 cm.-l for the carbonyls.340 Certain complexes can be formulated as containing the NO- group; these include the nitrosopentammine-, nitrosopentacyano-, and nitrosonitrito-cobalt ions.3q1 The first exists in two forms, red and black. The black form, previously thought to have an appreciable magnetic moment, is now known to be diamagnetic.3q2 It is therefore now feasible to regard the black compound as dimeric, with the two NO groups forming a hyponitrite structure, whereas the red form has an NO- structure.=l The paramagnetic species [Fe(H,O),N0I2 +, [Fe(NH,),N0I2', and [Fe(EtOH),N0J3+ have sp3d2 outer-orbital bonding with NO+ ~o-o rd ina t ion .~~ In the complex ion [Fe(CN),N0]3- the iron is in the iron(I1) state; nitric oxide co-ordinates to the metal by two electrons only, the odd electron remaining localized on the ligand.=, The structure [Fe(NO),]-NO+ was first suggested by Sidgwick for tetranitrosyl iron. The infrared spectrum indicates that three nitric oxide units bond as NO+ and one as NO-. The spectrum has two frequencies similar to those observed for Fe(NO),Cl, with which the suggested structure [Fe(NO),] +NO- is analogous.w The complex Ru,N,O,,, which is precipitated by reaction of nitric oxide with ruthenium tetroxide in carbon tetrachloride solution, was believed to be one of the few compounds containing bidentate nitrate groups; the structure (N03)2NO*Ru~O*Ru~NO*(N0,)2 was suggested. However, reactions of its aqueous solutions more nearly corre- spond with the presence of one nitrato-group per atom of ruthenium, and the structure (NO,) RuO,(NO) ,*O*(NO) ,O,Ru( NO,) is more probable.= Cryoscopic measurements with the complex K,[Ni(CN),NO] show it to be uninuclear. The corresponding carbonyl compound K,[Ni(CN),CO] derived from Belucci's salt is binuclear, so that conclusions as to the mode of nitric oxide bonding based on direct comparison of the two compounds as monomers are not justified.=

The structure of Roussin's black salt has been resolved by X-ray analysis of the salt CsFe,S,(NO),, H20. The atoms are arranged as in (27) and there are no bridging nitric oxide groups.346 The bonding of the three iron atoms at the base of the tetrahedron, and the 3-co-ordinate sulphur, are similar to those found in the red ethyl ester (28).347 The preferred electronic structure has four non-bonding electrons on each iron atom, and one electron pair in a highly delocalized molecular orbital among the four iron atoms, thus account- ing for the diamagnetism.346

(c) OleJin and acetylene complexes. A possible structure for the compound Fe2C1,,H,0, formed from acetylene and iron carbonyl hydride was given in Annual Reports for 1956 (p. 108). The problem has now been largely resolved by an X-ray determination of the structure of the analogous

341 W. P. Griffith, J. Lewis, and G. Wilkinson, J . Inorg. Nuclear Chem., 1958, 7, 38. 342 R. W. Asmussen, 0. Bostrup, and J. P. Jensen, Acla Chem. Scand., 1958, 12, 24. 333 W. P. Griffith, J. Lewis, and G. Wilkinson, J. , 1958, 99. 344 J. M. Fletcher, J . Inorg. Nuclear Chem., 1958,8,277; F . S . Martin, J. M. Fletcher,

345 R. Nast and H. Bohme, 2. Naturforsch., 1958, 13b, 625. 946 G. Johansson and W. N. Lipscomb, J . Chem. Phys., 1957, 27, 1417; Acta Cryst.,

347 J . T. Thomas, J. H. Robertson, and E. G. Cox, ibid., p. 599.

P. G. M. Brown, and B. M. Gatehouse, J . , 1959, 76.

1958, 11, 694.

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but-2-yne complex (29). One iron atom is in a five-membered ring; the second lies below this ring, and at a distance from it similar to that found in tetracarbonyldicyclopentadienyldi-iron. At the same time, an Fe-Fe bond is believed to exist.a8 Dimethylacetylene and iron pentacarbonyl react in sunlight to give orange crystals having the empirical

0 1 N I

Fe

0

0

formula Fe(CO),(MeCiCMe),. This is not an addition complex; acid treatment gives duroquinol, so that the compound is actually a x-complex of a quinone (30). The quinone skeleton is synthesised during complex formation, which offers a new preparative t e ~ h n i q u e . ~ ~ Iron tricarbonyl complexes with di- and tetra-phenylcyclopentadienone have been prepared in a similar way.%" Structure (31) has been proposed for the butadiene compound C,H,*Fe(CO),. Its spectral and other properties are very similar to those of tricarbonylcyclohexadieneiron. The metal-carbon bond en- visaged is more closely related to that in ferrocene than to those in the chelate complexes of non-conj ugated d i ~ l e f i n s . ~ ~ ~

More complex acetylides have been isolated. Complete replacement of cyano-groups occurs when K,[Ni(CN),] reacts in liquid ammonia with potassium salts of acetylene, propyne, and phenylacetylene, giving K,[Ni(C,R),]. From a suspension of anhydrous nickel cyanide in liquid ammonia, potassium phenylacetylide precipitates the tetrammine Ni(C2Ph),,4NH,.352 Following on the isolation of the tetra-ethynyl-

3*8 A. A. Hock and 0. S. Mills, Proc. Chem. SOC., 1958, 233. 349 H. W. Sternberg, R. Markby, and I. Wender, J . Amer. Chem. SOC., 1958, 80,

350 G. N. Schrauzer, Chem. and Ind., 1958, 1403, 1404. 351 B. F. Hallam and P. L. Pauson, J., 1958, 642. 352 R. Nast and H. Kasperl, 2. anorg. Chem., 1958, 295, 227; R. Nast, I<. \-ester,

1009.

and H. Griesshammer, Chem. Ber., 1957, 90, 2678.

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ADDISOS AND GREEKWOOD : THE TRAKSITION ELEMENTS. 151

manganate, K,[Mn(C,H),], the hydrogen acetylide itself has been prepared by the reaction Mn(SCN), + 2KC,H + 4NH3 + Mn(C,H),,4NH3 + 2KSCN in liquid ammonia and in the absence of air and moisture. In a high vacuum ammonia is lost, leaving black, explosive Mn(C,H),.353 Excess of potassium acetylide with cuprous iodide gives K,[Cu(C,H)J, but with molar quantities, dicopper acetylide is obtained crystalline.=

(d) Aromatic complexes. Tet racarbon ylc yclopen tadien ylvanadium can be reduced by sodium in liquid ammonia : 355

C,H,.V(CO), + 2Na Na,[C,H,.V(CO),] + C O

The product contains vanadium in the formal -1 state, and falls into the isoelectronic series [C5H5*V(C0)3]2-, [C,H,*Cr(CO),]-, [C,H,*Mn(CO),]. All carbonyl groups are removed in the reaction C,H,*V(CO), + 2HC1 + 0, _+

C,H,*VOCI, + 4CO + H,O; the blue-black, diamagnetic product is monomeric and s ~ b l i m a b l e . ~ ~

The yellow crystalline compound formed by reaction of sodium cyclo- pentadienide with rhenium pentachloride in tetrahydrofuran, followed by vacuum sublimation a t 120-200", is not the expected neutral (C,H,),Re, but the hydride (C,H,),ReH. In contrast to other known transition-metal complex hydrides, it behaves as a base weaker than ammonia and with acids formsS7 the cation [C,H,*ReH,]+. Reaction of carbon monoxide at 90" and 250 atm. pressure with the hydride gives3% the bright yellow, diamagnetic carbonyl (C,H,),ReH(CO),. Slightly different conditions lead to the formation of the tricarbonyl C,H,*Re(CO),, an air-stable yellow solid, m. p. 111-114", which is analogous to the manganese compound referred to above.359 Infrared and high-resolution nuclear magnetic resonance spectra of the compound (C,H,),ReH(CO), indicate that it is in fact di- carbonyl-n-cyclopentadienylcyclopen tadienerhenium (32). The hydrogen

atom originally regarded as bonded to the metal is located in the cyclopentadiene ring.360

Structure (33) has been confirmed for tetracarbonyldicylcopentadienyl- di-iron by X-ray crystallography. The proximity of the iron atoms

a53 R. Nast and H. Griesshammer, 2. anorg. Chem., 1958, 293, 322. 3,4 R. Nast and W. Pfab, ibid., 1957, 292, 287. S55 E. 0. Fischer and S. Vigoureux, Chem. Ber., 1958, 91, 2205. 356 Idem, ibid., p. 1342. 357 M. L. H. Green, L. Pratt, and G. Wilkinson, J. , 1958, 3916. 358 E. 0. Fischer and A. Wirzmuller, 2. Naturforsch., 1957, 12b, 737; see also E. 0.

359 R. L. Pruett and E. L. Morehouse, Chem. and Ind. , 1958, 980. 380 M. L. H. Green and G. Wilkinson, J., 1958, 4314.

Fischer, J . Inorg. Nuclear Chem., 1958, 8, 268.

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(2.49 A) indicates an Fe-Fe bond.361 The formation of dicyclopentadienyl- rhodium from ruthenocene by neutron bombardment

n. Y -B, Y 104R~(C5H5)2 __+c lo5Ru(C5H,), ___t 105Rh(C5H5)2

has been detected.362 The microwave spectrum of nitrosylcyclopentadi- enylnickel, C,H,*NiNO, can arise only if the Ni-N-O atoms are strictly linear and form an axis of symmetry normal to the cyclopentadiene ~lane.~63 Reaction between nickelocene and nickel carbonyl in benzene solution is as follows:

Ni(C5H5), + Ni(CO), --W [C,H,*NiCO], + 2CO

The red, diamagnetic nickel(1) product sublimes in vacuum at 80-90". This compound completes the series C,H,*V(CO),, [C5H5*Cr(CO),],, C,H,*Mn (CO),, [C,H,*Fe (CO) J2, C,H,*Co (CO),, [C,H,*NiCO],, each of which is diamagnetic. The nickel compound decomposes at high temperatures to give the dark green paramagnetic product (C,H,),Ni3(C0),.364

Triphenylchromium is obtained as the addition compound CrPh,(C,H,O),, a blood-red compound, by reaction of chromic chloride and phenylmagnesium bromide in tetrahydrofuran (C,H,O). I t is extremely sensitive to moisture. When heated, i t loses tetrahydrofuran; hydrolysis of the black residue gives dibenzenechromium and benzenediphenylchromium, which involves the unusual rearrangement of a covalently bonded phenyl group to a X-

complex.365 The addition compound 3LiPh,CrPh3,2.5Et,0 has also been prepared from chromic chloride and pheny l - l i t h i~m.~~~ Chromium(1) forms a mixed sandwich complex resembling the known manganese compound Mn(C,H,Me)C,H,. Chromic chloride is treated with equal molar quantities of phenyl- and cyclopentadienyl-magnesium bromide, and the orange , paramagnetic product Cr(C,H,) (C6H6) (m. p. 227') is obtained.,67 The reaction Cr(C,H,), + Cr(CO), + 2C6H6Cr(CO), proceeds in the presence of benzene at 220". Tricarbonylbenzenechromium (m. p. 162") sublimes in a vacuum at 60-90°.368 In a simpler, more general method, tricarbonyl derivatives of aromatic compounds can be prepared by heating chromium hexacarbonyl under reflux in excess of the aromatic compound, or with a molar quantity in an inert solvent a t 100-210". A wide range of aromatic compounds (Ar) can be used, including hydrocarbons, primary, secondary, and tertiary amines, and methyl benzoate. All products have the general formula ArCr(CO),. Molybdenum hexacarbonyl similarly gives a tricarbonyl derivative with mesit ylene .369

361 0. S. Mills, Acta Cryst., 1958, 11, 620. 362 F. Baumgartner, E. 0. Fischer, and U. Zahn, Chem. Ber., 1958, 91, 2336. 363 A. P. Cox, L. F. Thomas, and J. Sheridan, Nature, 1958, 181, 1157. 364 E. 0. Fischer and C. Palm, Chem. Ber., 1958, 91, 1725; see also E. 0. Fischer,

365 W. Herwig and H. H. Zeiss, J . Amer. Chem. SOC., 1957, 79, 6561. 368 F. Hein and R. Weiss, 2. anorg. Chem., 1958, 295, 145. 367 E. 0. Fischer and H. P. Kogler, 2. Naturforsch., 1958, lab, 197. 368 E. 0. Fischer and K. ofele, Chem. Ber., 1957, 90, 2532. 368 B. Nicholls and M. C. Whiting, Proc. Chem. SOC., 1958, 152; see also G. Natta,

R. Ercoli, and F. Calderazzo, Chimica e Industria, 1958, 40, 287; E. 0. Fischer, K. Ofele, H. Essler, W. Frohlich, J. P. Mortensen, and W. Semmlinger, 2. Naturforsch., 1958, 13b, 458.

J . Inorg. Nuclear Chem., 1958, 8, 268.

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ADDISON AND GREENWOOJ) THE TRANSITION ELEMENTS. 153

The field of metal-aromatic complexes has been extended to include a wider variety of aromatic systems. X-Ray analysis of di-indenyliron shows the iron atom to be situated between the five-membered rings, which are parallel and 3-43 A apart. The molecule has the gauche ~onfiguration.~~O Molybdenum carbonyl gives an azulene derivative C,,H,O,Mo, ; the molecule may consist of two Mo(CO), groups, one of which is bound to the seven- membered and one to the five-membered ring.371 With cycloheptatriene, an orange-red crystalline derivative C,H,Mo(CO), is obtained, rather than a tropylium compound. This sublimes in a vacuum at 85" and is believed to have the structure (34). The six x-electrons form a delocalized system which by-passes the methylene group.372 The corresponding tropylium ion complex has now been prepared, by treatment of compound (34) with triphenylmethyl fluoroborate, and isolated as the complex [(C,H,+)Mo(CO)J BF4-.373 Similar compounds have been obtained by reaction with iron

carbonyls. Dicarbonylcycloheptatrienyliron, C,H,Fe(CO), (b. p. 70°/0.4 mm.) , is a mobile, air-stable liquid. With azulene, pentacarbonylazulenedi- iron C,H,Fe,(CO), is formed as a red solid, which decomposes at 100" to give azulene again.374 Tricarbonylcycloheptatrienechromium has also been prepared, together with a number of compounds in which a substituent is present in the l-position in the cycloheptatriene ring. Prolonged reaction between dicycloheptatrienyl and molybdenum carbonyl produced the compound (35), and hexacarbonyl(dicycloheptatrieny1 ether) dimolybdenum has also been prepared.375 Reactions with platinum halides give the compounds [C,H,*PtBr,], 376 and (C,H,),PtC1,.575

Of particular interest is the formation of aromatic x-type complexes with heterocyclic compounds. Thiophen reacts with iron pentacarbonyl to give (C,H,S)Fe(CO),, m. p. 51", as pale red crystals soluble in most organic solvents and readily sublimable,374 and with chromium hexacarbonyl to give (C,H,S)Cr(CO),. The properties of the latter indicate that it has the structure (36) .377

The Scandium Group and Lanthanides.-Lanthanum dicarbide has a structure of the calcium carbide type, with C-C distance (1.28 A) intermediate between double and triple bond distances. However, its con-

370 J. Trotter, Acta Cryst., 1958, 11, 355. 371 R. Burton and G. Wilkinson, Chem. and Ind. , 1958, 1205. 372 E. W. Abel, M. A. Bennett, and G. Wilkinson, Proc. Chem. SOL, 1958, 152. 373 H. J. Dauben and L. R. Honnen. J . Amer. Chem. Soc., 1958, 80, 5570. 374 R. Burton, M. L. H. Green, E. W. Abel, and G. Wilkinson, Chem. and Ind., 1958,

575 E. W. Abel, M. A. Bennett, R. Burton, and G. Wilkinson, J., 1958, 4559. 376 E. 0. Fischer and H. P. Fritz, 2. phys. Chem. (Frankfurt), 1958, 17, 132. 377 E. 0. Fischer and K. ofele, Chem. Ber., 1958, 91, 2395.

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ductivity is comparable with that of lanthanum metal, whereas calcium carbide is an insulator. Since true salts of La2+ are unknown, lanthanum dicarbide can be described in terms of La3+C2,-, with the extra electron in a conduction band. The sesquicarbide La,C3 also contains C, ions and is a metallic conductor, though its conductivity is only half that of the dicarbide or the free A new carbide M3C has also been found which has the cubic sodium chloride type of structure except that it is deficient in carbon. It is found for elements M = Sm-Lu, but not when M = La, Ce, Pr, or Nd.379 The slight volatility of lanthanum butoxide La(OBut), indicates that it is polymeric.s0 Lanthanum rhodium oxide LaRhO, has a distorted perovskite structure.381 Oxide monosulphides M20,S have been prepared from sesquioxides by reaction with carbon disulphide or thioacetamide and subsequent reduction by hydrogen. Sm202S oxidizes at 620" in one step to Sm202*S04, a member of a new isostructural series of lanthanide compounds M202*S0,.382

The Titanium Group.-Modern techniques in the chemistry and metal- lurgy of titanium production have been reviewed.383 When ammonia gas is passed into a suspension of titanium trichloride in a mixture of benzene and acetylacetone, a dark blue hexaco-ordinated complex Ti(C,H,O,), separates which is sublimable in a vacuum.3M The related compound Ti(C,H,O,),Cl is probably dimeric, with chlorine bridging, thus retaining hexa-co-ordination.385 By reduction of a mixture of titanium tetrachloride and 2,2'-dipyridyl (dipy) in tetrahydrofuran with lithium, Ti(dipy), (violet needles) and LiTi(dipy),,3-5C4H,O (black plates) are obtained; physical properties confirm that they are compounds of titanium(0) and titanium( - I), respectively.386 Normal titanium sulphate, Ti(SO,),, is formed by reaction of titanium tetrachloride with sulphur trioxide :

TiCI, + 6S0, __t Ti(SO,), + 2S,0,C12

Parachors derived from densities and surface tensions of monomeric tertiary alkoxides of Ti, Zr, Sn, Ce, and Th indicate considerable intramolecular congestion, accentuated by metal-oxygen bond contraction388 Vapour pressures of titanium tetra-t-butoxide and -pentyloxide have been measured with precision ; 389 the apparatus incorporates a new double-spoon pressure gauge.390 Reactions involving a chloro-alcohol, chloro-aldehyde , or chloroalkanecarboxylate have been used to prepare chloro-alkoxides of Ti,

378 M. Atoji, K. Gschneidner, A. H. Daane, R. E. Rundle, and F. H. Spedding, J .

379 F. H. Spedding, K. Gschneidner, and A. H. Daane, ibid., p. 4499. 380 D. C . Bradley and M. M. Faktor, Chem. and Ind. , 1958, 1332. 381 A. Wold, B. Post, and E. Banks, J . Amer. Chem. SOC., 1957, 79, 6365. 382 H. A. Eick, ibid., 1958, 80, 43. 383 J. J. Gray and A. Carter, Roy. Inst . Chem. Monographs, 1958, No. 1. 384 B. N. Chakravarti, Naturwiss., 1958, 45, 286. 385 A. Pflugmacher, H. J. Carduck, and M. Zucketto, ibid., p. 490. 386 S. Herzog and R. Taube, Angew. Chem., 1958, 70, 469. 387 V. G. Chukhlantsev, Zhur. neorg. Khim., 1957, 2, 2014. 388 D. C. Bradley, C. C. A. Prevedorou, J. D. Swanwick, and W. Wardlaw, J., 1958,

389 D. C. Bradley and J. D. Swanwick, J. , 1958, 3207. 390 J. D. Swanwick, J. , 1958, 3214.

Amer. Chem. SOC., 1958, 80, 1804.

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ADDISON AND GREENWOOD: THE TRANSITION ELEMENTS. 155

Zr, Ce, and Th, e.g., M(OX), and MCL(OX),, where X = CC1,-CMe2.391 Zirconium forms a series of stable double alkoxides MZr(OR),, where R = Prn, Pri, Bun, and Bus, and M = Li, Na, or K. Many sublime or distil unchanged under reduced pressure.392 Complexes of titanium tetrafluoride, tetrabromide, and tetraiodide with various organic ligands (e.g., pyridine, nitriles) have been compared in stability with the known titanium tetrachloride complexes; those of the tetraiodide are least readily formed. For a given ligand and halide, the dissociation pressure is higher for the zircon-

ium than the titanium complex.393 The complex (C5H5)2TiCI,A1(C2H,)2 shows catalytic activity in

,cl, /Et ethylene polymerization ; from X-ray examination the structure is that shown in (37).394 BTi 'Et The interaction of the intermetallic compound ZrNi with hydrogen bears no resemblance to the zirconium-hydrogen system. The alloy forms a

definite hydride at a limiting composition ZrNiH,, and possibly a second hydride ZrNiH.395 A technique has been developed which enables a powdered zirconium-oxygen flame to be operated. The flame temperature, 4930" K at 1 atm. pressure, is the highest metal flame temperature recorded to date.Sg6 X-Ray diffraction of thorium germanides indicates at least six germanide phases. The phase of highest germanium content is ThGe(,.,+_,.,,. Tetragonal a-ThGe, is isostructural with a-ThSi,. The compounds ThGe and Th,Ge, are also discussed.3g7 In the acetylacetone complex Th(C5H,02),, the eight co-ordinating oxygen atoms form a square antiprism around the

The Vanadium Group.-The hydrated oxides of niobium(v) and tantalum(v) (niobic and tantalic acids) will give water-soluble complexes with a variety of a-hydroxy-acids, which may be phenolic or carboxylic. Niobic acid has a much greater solubility than tantalic acid in these solutions, but when the two acids are coprecipitated, part of the tantalum is carried into solution with the niobium as a result of the multinuclear character of the complexes.399 Thermal and X-ray analysis of the system Na,O-Nb,O, show the existence 400 of four compounds Na,O, 14Nb20,, Na20,4Nb,05, Na20 ,N b205 and 3Na20 ,Nb,O,. Vanadium tetrachloride reacts with alcohols in cold benzene forming compounds VCl,(OR),,ROH (R = Me, Et, Pr, Bu, or n-pentyl). On heating these products under vacuum at 150°,

A1 .G?

(37)

391 D. C. Bradley, R. N. P. Sinha, and W. Wardlaw, J . , 1958, 4651; see also A. M.

392 W. G. Bartley and W. Wardlaw, J. , 1958, 422. ss3 H. J. Emeldus and G. S. Rao, J. , 1958, 4245; see also J. Archambault and R.

394 G. Natta, P. Corradini, and I. W. Bassi, J . Amer. Chem. SOC., 1958, 80, 755. 395 G. G. Libowitz, H. F. Hayes, and T. R. P. Gibb, J . Phys. Chem., 1958, 62, 76. 396 W. L. Doyle, J. B. Conway, and A. lT. Grosse, J , Inorg. Nuclear Chem., 1958,

397 A. G. Tharp, A. W. Searcy, and H. Nowotny, J . Electrochem. SOC., 1958, 105,

398 D. GrdeniC and B. Matkovie, Nature, 1958, 182, 465. 399 F. Fairbrother, D. Robinson, and J. B. Taylor, J . Inorg. Nuclear Chem., 1958, 8,

400 A. Reisman, F. Holtzberg, and E. Banks, J . Amer. Chem. SOC., 1958, 80, 37.

El-Aggan, D. C. Bradley, and W. Wardlaw, J. , 1958, 4643.

Rivest, Canad. J . Chem., 1958, 36, 1461; R. Aubin and R. Rivest, ibid., p. 915.

6, 138.

473.

296; J., 1958, 2074.

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conversion into vanadium oxychloride alkoxides V,OCl,(OR), occurs. Molybdenum pentachloride reacts similarly.401 Volatile mixed alkoxides of tantalum Ta(OR)(OR'), are formed provided that R' is a branched alkyl

Vanadium pentafluoride reacts with nitryl fluoride to form involatile, white N0,VF6, and with nitrosyl fluoride to give the nitrosonium salt NOoVF,. The corresponding hexafluoroniobates and hexafluorotantalates are best prepared by reaction of the metal pentoxide and bromine trifluoride with dinitrogen tetroxide or nitrosyl chloride. Chloryl hexafluorovanadate is stable only at low temperatures. Vanadium pentafluoride is converted by sulphur dioxide or trioxide into the oxyfluoride VOF,; in contrast, niobium and tantalum pentafluorides give addition compounds formulated as fluorosulphates e.g., NbF,(SO,F),. Direct action of pyridine with the pentafluorides also yields addition compounds, e.g., (C,H,N),NbF,. These are white solids, stable in air and readily soluble in ~ a t e r . ~ W Ruff and Lickfett in 1911 reported vanadium oxytrifluoride as having m. p. 300", b. p. 480". The vapour pressure has now been measured from 72.1" (122.7 mm.) to 122.8" (1519 mm.) ; the vapour pressure of the solid reaches 760 mm. at 110", so that the compound is much more volatile than was previously reported. There is no melting or solid transition between 72" and 123°.404 The preparation of some addition compounds of vanadium oxytrichloride (e.g., VOC1,,2X, where X = an amine or nitrile) and substitution compounds (e.g., chloride alkoxides) has been described.405 Vanad- ium(1v) chloride undergoes partial solvolysis in liquid ammonia to give the compound VCl(NH,),. The solubility of the latter in liquid ammonia containing ammonium chloride is attributed to ionic species of the type NH,vC12(NH,),].QOG Niobium and tantalum pentachlorides and penta- bromides form 1 : 1 complexes with diethyl ether which decompose at 100" into ethyl halide and metal oxytrihalide; tantalum pentaiodide does not form an ether complex.407

Although niobium pentachloride and pentabromide exist as monomeric trigonal bipyramidal NbC1, and NbBr, molecules in the vapour, the solid chloride consists of dimers Nb,ClIo, with two chlorine atoms bridging two octahedra. NbBr, and TaC1, appear to be isomorphous with this structure.408 Conditions have been reported for the preparation and sublimation of niobium(1v) iodide by thermal decomposition of the pentaiodide, and for subsequent disproportionation to give niobium(Ir1) iodide. The grey tetraiodide, like the pentaiodide, is extremely sensitive to water and oxygen, whereas the black tri-iodide is stable to air.409 Niobium tri- iodide, prepared from aluminium iodide and niobium pentoxide, has been

401 D. C. Bradley, R. K. Multani, and W. Wardlaw, J., 1958, 4647. 402 D. C. Bradley, B. N. Chakravarti, A. K. Chatterjee, W. Wardlaw, and -4. Whitley,

408 H. C. Clark and H. J. EmelCus, J., 1958, 190. 404 L. E. Trevorrow, J. Phys. Chem., 1958, 62, 362. 405 H. Funk, W. Weiss, and M. Zeising, 2. anorg. Chem., 1958, 296, 36. 408 G. W. A. Fowles and D. Nicholls, J., 1958, 1687. 407 A. Cowley, F. Fairbrother, and N. Scott, J., 1958, 3133. 408 A. Zalkin and D. E. Sands, Acta Cryst., 1958, 11, 615. 409 J. D. Corbett and P. X. Seabaugh, J. Inorg. Nudear Chem., 1958, 6, 207.

group.402

J., 1958, 99.

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reduced in a current of hydrogen at 300" to the d i - i ~ d i d e . ~ ~ ~ The mixed halides NbBrI,, TaBr,I, and TaBrI, have been produced by reaction of an aluminium bromide-iodide mixture with niobium or tantalum ~entoxide.~l l

Recent developments in the chemistry of protactinium and neighbouring elements have been reviewed.412 A detailed examination has been made of the factors influencing the extraction of protactinium from chloride solutions by a number of organic solvents. Results can be explained in terms of the distribution of an ion-pair complex formed by a chloro-anion containing the metal, and an " onium " cation containing water and solvent m0lecules.4~~ In nitric acid solutions the protactinium species consist of a series of hydroxo- nitrat o-complexes .414

The Chromium Group.-The chemistry of chromyl compounds has been reviewed.415 New chromyl compounds include chromyl fluoride chloride,416 and chromyl acetate (m. p. 30.5°).a7 Chromous acetylacetone (m. p. 218") is obtained as a yellow powder from chromous acetate and acetylacetone in sealed apparatus under pure nitrogen. It is oxidized vigorously in air, and may ignite in oxygen.418 The reaction Cr,O,,- + ZNO,- _t N,O, + 2Cr0,2-, followed by N,O, + 2N0, + 402, proceeds at a measurable rate in fused potassium nitrate-sodium nitrate eutectic mixture a t 250°.41s Blue complexes of chromium(II1) with o-phenylenebisdimethylarsine are non- electrolytes of the type [Cr(diarsine)X,,H,O], where X is a halogen. From green complexes [Cr(diarsine),X,] [Cr(diarsine) X,] the perchlorate [Cr(diarsine),X,]ClO, is readily isolated. The magnetic moment of each compound is near 3.9 B.M., indicating that electron pairing has not taken place.420 No diarsine complex containing three molecules of ligand co- ordinated to a single chromium atom was obtained,420 but the ligand 2,2'- dipyridyl forms the complex [Cr(dipy),].

Proton magnetic resonance and infrared measurements show that the yellow solid which slowly separates from a nitric acid solution of ammonium molybdate is the hydrate MoO3,2H,O, and not MoO,(OH),,H,O or (H,0)2+Mo0,2-. A monohydrate MoO,,H,O is also confirmed.42" Several equilibria are involved in the vaporization of the oxides MOO,, Mo,O1,, MOO,, WO,, and WO, at high temperatures. The trioxide vaporizes to the trimer (MOO,)&), while Mo,O,,(s) disproportionates to (MoO,),(g) and MoO,(s) ; the latter disproportionates further to (MOO,), and Mo(s). The tungsten oxides behave similarly.423 Both 3 : 12- and 1 : 12-heteropoly-

410 M. Chaigneau, Corn@. rend., 1957, 245, 1806. 411 Idem, ibid., 1958, 247, 300. 412 A. G. Maddock, X VI Internat. Congr. Pure A#. Chew., Experieittia Szcppl.

413 A. G. Goble and A. G. Maddock, J . Inorg. Nuclear Chem., 1958, 7 , 94. 414 C. J. Hardy, D. Scargill, and J. M. Fletcher, ibid., p. 257. 415 W. H. Hartford and M. Damn, Chem. Rev., 1958, 58, 1. 416 G. D. Flesch and H. J. Svec, J . Amer. Chem. Soc., 1958, 80, 3189. 417 H. L. Krauss, Angew. Chem., 1958, 70, S02. 418 G. Costa and A. Puxeddu, J . Inorg. Nuclear Chem., 1958, 8, 104. 419 F. R. Duke and M. L. Iverson, J . Amer. Chem. Soc., 1958, 80, 5061. 420 R. S. Nyholm and G. J. Sutton, J., 1958, 560. 421 S. Herzog, I<. C. Renner, and W. Schon, 2. Naturforsch., 1957, 12b, 809. 422 S. MariEiC and J. A. S. Smith, J. , 1958, 886. 423 P. E. Blackburn, M. Hod , and H. L. Johnston, J . Plzys. Clzem., 1958, 62, 769.

V I I , 1957, 213.

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acids of zinc with tungstate have been recognized. The chemistry of 12-tungstozincic acid and its salts resembles that of 12-tungstophosphoric acid. The structure is similar but with zinc replacing phosphorus as the central atom.424 A white cyano-complex of molybdenum(Iv), KMo(CN),, is prepared directly from potassium cyanide and molybdenum trioxide, or from other cyano-complexes. The anion is uninuclear, and the molybdenum atom believed to be penta~o-ordinate .~~~

Tungsten hexafluoride reacts with sulphur trioxide to give the fluoro- sulphate WF,(SO,F),. With ammonia the tetra-ammine WF,(NH,), is formed, and similar addition compounds WF,(C,H,N), and WF,(CH,*NH,), are formed with pyridine and with methylamine. Pure tungsten hexafluoride does not react with alkali-metal fluorides under strictly anhydrous and grease-free conditions.426 The higher complex fluorides of tungsten (VI) are best prepared by addition of excess of the hexafluoride to the alkali iodide in the presence of iodine pentafluoride. The compounds K2WF,, K,WF,, RbWF,, CsWF,, and CsWOF, have been characterized, and an analogous series of molybdenum fluoro-complexes obtained by similar reactions. Magnetic properties of the complex fluorides MMoF,, MWF,, and MReF, (M = alkali metal) have been compared.427

The infrared spectrum of uranyl nitrate hexahydrate is typical of an ionic nitrate. However, the spectra of the di- and tri-hydrate are similar to that of rubidium uranyl nitrate, and are characteristic of compounds having co-ordinated nitrate groups. In the structures postulated for these lower hydrates some of the nitrate groups act as bidentate ligands.428 Uranium tetrachloride forms addition compounds with amines and ammonia, of general formula UCl,,nRNH,. When R = H, Me, Et, then n = 2, 2, and 1 or 2, respectively. A hydrazine addition compound UC14,6N2H, has also been identified.429 Phase equilibria in the systems NaF-ZrF,, UF4-ZrF,, and NaF-ZrF4-UF4 have been examined in detail. The uranium systems are of interest as potential fuels in fluid reactors.&O

The Transuranium Elements.-Reviews on recent research on the actinide elements,&l and on the transuranic elementsJa2 have been published during the year. Reversible equilibrium amongst the four oxidation states of plutonium is maintained at all times, but reaction between Pu3+ and Pu022+ is demonstrably slow. The kinetics of the reaction Pu3+ + Pu022+ Pu4+ + PuO,' have been studied spectrophotometrically, the PuO,2+ absorption peak at 8304 crn.-l being used. Reaction rate is independent of hydrogen-ion concentration.= With vanadium(II1) in place

424 D. H. Brown and J. A. Mair, J. , 1958, 2597. 425 M. C. Steele, Austral. J . Chem., 1957, 10, 404. 426 H. C. Clark and H. J. EmelCus, J. , 1957, 4778. 427 G. B. Hargreaves and R. D. Peacock, J. , 1958, 2170, 3776, 4390. 428 B. M. Gatehouse and A. E. Comyns, J. , 1958, 3965. 429 I. Kalnins and G. Gibson, J . Inorg. Nuclear Chem., 1958, 7 , 56. 430 C. J. Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, J . phys.

Chem., 1958, 62, 665; see also C. J. Barton, H. A. Friedman, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, J . Amer. Ceram. SOC., 1958, 41, 55.

431 G. T. Seaborg, X V I Internal. Congr. Pure AppZ. Chem., Experientia Suppl. V I I , 1957, 63.

432 H. J. EmelCus, Chem. and Iitd., 1958, 1276. 493 S. W. Kabideau and R. J. Mine, J . Phys. Clrcnz., 1958, 62, 617.

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ADDISON A N D G R E E N W O O D : T H E TRANSITIOPU' ELEMENTS. 159

of plutonium(m), the stoicheiometry of the reaction is PuO,2+ + V3+ + H20 + Pu02+ + V02+ + 2H+.434 Other reactions for which kinetics and mechanism have been examined include neptunium (111)-neptunium(v) plutonium(v1)-uranium(1v) ,m6 and the reduction of neptunium(v1) to neptunium(v) by hydrogen peroxide.m7

Partition coefficients have now been determined for (Th, Np, Pu) (NO,), and (U, Np, Pu)O,(NO,), between aqueous nitric acid and tri-n-butyl phosphate (TBP). All are strongly extracted, and form disolvates M (NO,),, 2TBP and MO, (NO,) ,, 2TBP.a Absorption spectra of plu tony1 nitrate in dibutylcarbitol show the presence of both the dinitrate and the trinitrate. The latter has a much higher partition coefficient for extraction from nitric acid solution, and is formed preferentially. The association constant for the reaction PuO,(NO,), + HNO, --w HPuO,(NO,), is 4 & l.439 All the plutonium(1v) present in nitrate solutions above 1 ~ - concentration, or in 1AM-nitric acid, is in the form of undissociated Pu(NO,),. The only plutonium(1v) species present in concentrated nitric acid is HzP~(N0,),.440 A solution containing plutonium in the plutonium- (v) state only has been prepared by mixing equal quantities of plutonium(II1) and plutonium(v1) in 0.2~-nitric acid. The reaction PU(III) + PU(VI) _t

PU(IV) + Pu(v) occurs; the plutonium(1v) is extracted into dibutyl hydrogen phosphate in benzene, leaving plutonium(v) in the aqueous phase .*l

Anhydrous plutonium(1v) sulphate is not a suitable form in which plutonium can be weighed in gravimetric analysis, since its composition varies slightly with the temperature a t which it is prepared from the hydrate. Dilute aqueous solutions become turbid a t a rate which depends on concentration. An anionic complex is probably formed by sulphate ions liberated by hydrolysis; electromigration experiments on a solution of the sulphate in water revealed the presence of much anionic, but negligible cationic, plutonium.u2 Ozone converts plutonium(1v) into plutonium(v1) in macro-concentration in dilute sulphuric acid and in the absence of catalysts, thus permitting preparation of pure plutonium(v1) sulphate solutions. The rate of oxidation is much slower than in dilute nitric or perchloric acid, owing to increased stabilization of plutonium(1v) by sulphate complex formation.443 Studies have been made of equilibria involving oxalate complexes of plutonium(II1) ,444 the plutonium( IV) oxalate complexes [Pu (C,O,) I,+-, [PU(C,O,),]~, [Pu(C,O,),]~-, and [PU(C~O,),]~-, plutonium(1v) carbonate

434 S. W. Rabideau, J . Phys. Chem., 1958, 62, 414. 435 J. C. Hindman, J. C. Sullivan, and D. Cohen, J . Amer. Chem. SOC., 1958,80, 1812. 436 T. W. Newton, J . Phys. Chem., 1958, 62, 943. 437 A. J. Zielen, J. C. Sullivan, D. Cohen, and J. C. Hindman, J . Amer. Chem. SOC.,

438 I<. Alcock, G. F. Best, E. Hesford, and H. A. C. McKay, J . Inorg. Nuclear Chem.,

439 T. V. Healy and A. W. Gardner, ibid., 1968, 7, 245. 440 J. A. Brothers, R. G. Hart, and W. G. Mathers, ibid., p . 85. 4 4 1 T. L. Markin and H. A. C. McKay, ibid., p . 298. 442 J. L. Drummond and G. A. Welch, J. , 1958, 3218. 443 D. W. Grant, J . Inorg. Nuclear Chem., 1958, 6, 69. 444 A. D. Gel'man, N. N. hlatorina, and A . I. Moskvin, Doklady Akad. Naitk S.S.S.R.,

1958, 80, 5632.

1958, 6, 328; T. Sato, ibid. , p . 334.

1957, 117, 88.

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c ~ m p l e x e s , ~ ~ and oxalate and carbonate complexes of the plutonium(v1) species.M6 Methods for the preparation of two new plutonium phosphates PuPO, and PuP,O, employ plutonium oxalatophosphates as inter- med ia t e~ .~ ' Plutonium dioxide has a formula in the range PuO,,,.,, depending on starting material and ignition temperature. Thus the product made by ignition at 1200" is stoicheiometric; that made by ignition of plutonium salts in air a t 870" has a higher molecular weight. Plutonium metal or its hydride reacts with graphite at 900" to give the monocarbide PuC. A sesquicarbide Pu,C, was also formed when the oxide PuO, was reduced by graphite at 1800". Both carbides are easily hydrolysed by boiling water or dilute acid.448 Conditions for the preparation of neptunium oxides have been modified and improved.449 A technique being used which permits spectral examination of submilligram amounts of solids, the absorption spectra of curium(Iv) fluoride and americium(rv) fluoride have been measured for comparison with spectra of the trifluorides of these e1ements.m The ion-exchange behaviour, and dissociation constants, of EDTA complexes of americium, curium, and californium show that EDTA is a useful separating agent.451 Americium oxalate, dried in a vacuum at room temperature, exists as the heptahydrate. When heated in air this passes through the 4-, 3-, 1-, and 06hydrates, giving the anhydrous oxalate at 240". Conversion into the dioxide is complete at 470", with no evidence for carbonate formation during final decomposition. In vacuum, decomposition to the sesquioxide Am,O, occurs.452

It is reported that in many scores of experiments, workers at Berkeley, California, have been unable to repeat the preparation of the 251 or 253 isotope of element 102 (having a-activity of 8-5 MeV) claimed to have been produced by bombarding 244Cm with 90-Mev ions of 13C4+. The claim to have prepared nobelium by this method is therefore disputed. More recent experiments, using the new Berkeley heavy-ion linear accelerator, have produced *NO, an or-emitter. The daughter element 250Fm is separated 453 by taking advantage of recoil on decay of 254No. Helium-ion bombardment of WEs has led to identification of a new isotope 255Md. This has a half-life of about Q

The Manganese Group.-The mechanism of oxidation by compounds of manganese 4 5 5 ~ ~ and of chromium 455 has been reviewed. Manganese(I1) forms compounds [Mn(diarsine),XJ with o-phenylenebisdimethylarsine,

445 A. D. Gel'man and A. I. Moskvin, Doklady Akad. Nauk S.S.S.H., 1958, 118, 493; Zhur. neorg. Khim., 1958, 3, 956, 962.

446 A. D. Gel'man and L. E. Drabkina, ibid., p. 1105; L. Drabkina, ibid., p. 1109. 447 C. W. Bjorklund, J. Amer. Chem. SOL, 1957, 79, 6347. 448 J . L. Drummond and G . A. Welch, J., 1957, 4781; J. L. Drummond, B. J.

McDonald, H. M. Ockenden, and G. A. Welch, J., 1957, 4785. 44s D. A. Collins and G. M. Phillips, J. Inorg. Nuclear Chem., 1958, 6, 67. 450 W. T. Carnall, P. R. Fields, D. C. Stewart, and T. K. Keenan, ibid., p. 213;

L. B. Asprey and T. K. Keenan, ibid., 1958, 7, 27. 451 J. Fuger, ibid., 1958, 5, 332. 463 T. L. Markin, ibid., 1958, 7, 290. 455 A. Ghiorso, T. Sikkeland, J. R. Walton, and G. T. Seaborg, Phys. Rev. Letters,

454 L. Phillips, R. Gatti, A. Chesne, L. Muga, and S. Thompson, ibid., p. 215. 455 W. A. Waters, Quart. Rev., 1958, 12, 277. 456 J. W. Ladbury and C. F. Cullis, Chem. Rev., 1958, 58, 403.

and decays by orbital electron capture to 255Fm.

1958, 1, 17, 18.

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ADDISON AND GREENWOOD THE TRANSITION ELEMENTS. 161

(X = halogen). A red manganese(II1) complex [Mn(diarsine)Cl,,H,O]C10, contains four unpaired electrons.s7 Rhenium(II1) complexes of the type [Re(diarsine),X,]ClO, are prepared by heating under reflux per-rhenic acid, the diarsine, hypophosphorous acid, and the appropriate halogen acid in alcohol. Vigorous reduction of the rhenium(II1) complexes, e.g. , with sodium stannite, gives rhenium(I1) complexes [Re(diarsine),X,] ?58 Oxidation by chlorine or bromine gives the new complex [Re(diarsine),Cl,]ClO,; the octaco-ordination of the rhenium(v) atom is of particular interest.459 Potassium octacyanorhenate(v) K,[Re(CN),] and the rhenium(v1) compound K,[Re(CN),] show this octaco-ordination and, with the exception of the well-known molybdenum and tungsten compounds, they are the only octaco-ordinated cyanides so far reported.460

Rhenium mono- and tri-iodides have been identified as decomposition products of the tetraiodide. The reduction of per-rhenic acid by hydriodic acid gives black rhenium tetraiodide; the tri-iodide is a black crystalline solid obtained by heating the tetraiodide in a sealed tube at 350". When heated to constant weight at 110" in a stream of nitrogen the tetraiodide gives the monoiodide ReI, which when heated further in a vacuum decomposes to the free Ammonium hexaiodorhenate(1v) decomposes to rhenium metal at 700" in a vacuum.462 Per-rhenyl fluoride Re0,F is obtained in good yield by the reaction 463 KReO, + IF, = Re0,F + IOF, + KF. Complexes of rhenium dichloride with water, hydrogen chloride , pyridine, and acetic acid have been de~cribed.,~

Potassium pertechnetate may be converted into hexahalogeno-complexes by the following series of reactions:

HCI HEr HI KTcO, --+ K2TcCI, __t K,TcBr, __t K,Tcl,

KI

The magnetic susceptibility, absorption spectra, and crystal structures of these compounds resemble closely those of the corresponding rhenium compound^.^^

The Iron Group.-Nine primary alkoxides of iron, Fe(OR),, have been prepared either from ferric chloride, the alcohol, and ammonia, or by alcohol interchange. All except the methoxide volatilize unchanged in a vacuum. The normal alkoxides Fe(O*C,H,,+,),, where 'yt = 1-5, are trimers in boiling benzene, but that of neopentyl oxide is dimeric. The influence of chain structure has been studied for ten further branched-chain alkoxides?66 Iron(1v) nitrilotriethoxide is obtained by the reaction NH4FeCl, + (HO*C,HJ,N,HCl + 4NH, _t Fe(O*C,H,),N + 5NH4C1. On addition of ether to the solution, green crystals of the monohydrate separate, and

457 R. S. Nyholm and G. J. Sutton, J., 1958, 564. 458 N. F. Curtis, J. E. Fergusson, and R. S. Nyholm, Chern. and Ind., 1958, 625. 459 J. E. Fergusson and R. S. Nyholm, ibid., p. 1555. 480 R. Colton, R. D. Peacock, and G. Wilkinson, Natuve, 1958, 182, 393.

R. D. Peacock, A. J. E. Welch, and L. F. Wilson, J., 1958, 2901. 462 A. A. Woolf, J . Inorg. Nuclear Chem., 1958, 7, 291. 463 E. E. Aynsley and M. L. Hair, J., 1958, 3747. 464 A. S. Kotel'nikova and V. G. Tronev, Zhur. neorg. Khim., 1958, 3, 1008. 465 J. Dalziel, N. S. Gill, R. S. Nyholm, and R. D. Peacock, J., 1958, 4012. 466 D. C. Bradley, R. K. Multani, and W. Wardlaw, J., 1958, 126, 4153.

REP.-VOL. LV F

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evaporation of a solution of the hydrate gives the anhydrous compound. It is polymeric, like the aluminium compound.467 Iron exists in mixed oxidation states in the fluoride Fe2F5,7H,0 (rFeF,,FeF3,7H,0). When heated at 100" this yellow hydrate is converted into the red trihydrate Fe,F5,3H,0, and at 180" into blue-grey anhydrous Fe,F,.468 The phase diagram for the system FeC1,-KCl shows two compounds: KFeCl,, congruent m. p. 399", and K,FeCl,, incongruent m. p. 380".469 A mass-spectrometric study shows that at low temperatures (650" K) the vapour of ferrous chloride is mainly monomeric, though the quantity of dimer Fe,Cl, increases rapidly with temperature.470 When ferrous chloride is kept a t 250-300" in an atmosphere of bromine, sublimation occurs, and mixed halide molecules form the major species in the vapour phase.471

The ruthenium@) species Ru3+, RuC12+, and RuCl,+ have been characterized in aqueous solution, ion-exchange resins being Ruthen- ium(I1) complexes with o-phenylenebisdimethylarsine, [Ru(diarsine),XJ, resemble those formed by manganese@). Oxidation gives ruthenium(II1) complexes containing the cation [Ru(diarsine),XJ+, which resist further oxidation. Osmium forms analogous complexes which can be oxidized by nitric acid to osmium(1v) compounds, e.g., [Os(diarsine),XJ (c104),.473 The infrared spectrum of potassium osmiamate K[OsO,N] confirms that the anion is a distorted tetrahedron, with three 0s -O bonds and one Os-N bond. Both this compound and potassium nitrilopentachloro-osmate, K,[OsCl,N] , are diamagnetic.,7, Neither metallic ruthenium or osmium, nor their dioxides, react with phosphorus trifluoride, but the tetroxides readily react. Ruthenium tetroxide gives (RuO,),,PF, a t -lOO", and Ru04,PF3 a t 20". Osmium tetroxide behaves similarly, except that the compound (OsO,),,PF, must be heated to 70" before further addition of fluoride occurs. The compounds are black and very hygroscopic. By contrast, phosphorus trichloride and tribromide reduce ruthenium tetroxide to give RuO,,PCl, and RuO,,PBr, ; osmium tetroxide is reduced by phosphorus trichloride to OSO,,PC~,.~~~ Aqueous solutions of the acid H,0sF6 have been prepared by ion-exchange methods, and from the solution those salts M,OsF, (M = NH,, NMe,, Na) may be obtained which are not readily available by alternative routes. Iridium compounds behave similarly.476

The most volatile product of the reaction between osmium metal and fluorine gas was first described in 1913 by Ruff and Tschirch as having m. p. 32.1", b. p. 45.9", and was identified as osmium octafluoride. The synthesis has now been re-examined. Molecular-weight determinations and chemical analysis of a product having identical physical properties leave no doubt that it is the hexafluoride OsF,, rather than OsF,. This is supported by

467 K. Starke, J. Inorg. Nuclear Chem., 1958, 6, 130. 468 G. Brauer and M. Eichner, 2. anorg. Chem., 1958, 296, 13. 469 H. L. Pinch and J. M. Hirshon, J. Amer. Chem. Soc., 1957, 79, 6149. 470 R. C. Schoonmaker and R. F. Porter, J. Chem. Phys., 1958, 29, 116. 471 L. E. Wilson and N. W. Gregory, J . Amer. Chem. Soc., 1958, 80, 2067. 472 H. H. Cady and R. E. Connick, ibid., p. 2646. 478 R. S. Nyholm and G. J. Sutton, J., 1958, 567, 572. 474 J . Lewis and G. Wilkinson, J. Inorg. Nuclear Chem., 1958, 6, 12. 475 M. L. Hair and P. L. Robinson, J., 1958, 106. 476 M. A. Hepworth, P. L. Robinson, and G. J, Westland, J., 1968, 611.

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X-ray diffraction, and by infrared and Raman spectroscopy. The octafluoride has had a significant place in chemical theory, so that it is important to note that the compound known for many years as the octafluoride is in fact the h e ~ a f l u o r i d e . ~ ~ ~

The Cobalt Group.-By the reaction [Co(NH,),]X, + 3KPH2 __t

Co(PH,), + 3KX + 6NH, (where X = NO, or I), a cobalt derivative of phosphine is obtained which is analogous to the metal amide. This is strongly pyrophoric and decomposes spontaneously at 0" : Co(PH,), __t

Co(PH), + 14H2. This second product is highly polymeric.478 Durrant's salt, K,[Co(C,O,),OH,H,O], has a bridged and binuclear structure. It is formed from cobalt(I1) solutions in excess of oxalate by the action of oxygen- carrying oxidants (H,O,, OCl-) . The one-electron oxidant Ce4+ gives 479

instead [c0(c,o,),]3-. Complexes of the cobalt cyanides Co(CN),, Co,(CN),, and Co(CN), with dipyridyl and with phenanthroline have been described.ao Rhodium and iridium form complexes in which a low valency is stabilized by 2,2'-dipyridyl, and thus resemble cobalt. For example, reduction of the complex [Rh(dipy),] (ClO,), by borohydrides, sodium amalgam, or zinc amalgam gives the bisdipyridyl salt [Rh(dipy),]C10,,3H,0.af In spite of previous statements, there is now evidence from spectrophotometry that a complex is formed in solution between EDTA and anionic rhodium( 111) .482

New hexaco-ordinated iridium complexes containing unidentate SOZ- groups, e.g., [Ir(S0,),C1,]5- and [Ir(S0,),(NH3)4]-, have been described.483

The Nickel Group.-The factors which determine the formation of tetrahedral nickel(I1) complexes are now better understood as a result of experiments on bistriphenylphosphine complexes. It was already known that the complexes (Et,P),NiX, (X = C1, Br, I) were diamagnetic, with trans-planar structure, while (Et,P),Ni(NOJ, was paramagnetic and possibly tetrahedral. The complexes (Ph,P),NiX, (X = C1, Br, I, NO,) are now found to be paramagnetic and tetrahedral, although (Ph,P),Ni(SCN), is diamagnetic and probably trans-square planar. In general, tetrahedral complexes of nickel@) are formed only when ligands have insufficient perturbing power to give rise to spin-pairing, and when the steric requirements of the ligands favour this ~ t r u c t u r e . ~ ~ The complex Ni(en),(NCS), is blue and paramagnetic, but the co-ordination of the nickel ion is trans-octahedral, with Ni-N distances of 2-10 A to the ethylenediamine and 2.15 A to the isothiocyanate. A co-ordination octahedron also exists in [Ni(en) (H,O),] (NO,),, which is again blue and paramagnetic.485 This would indicate that the blue

477 B. Weinstoclc and J. G. Malm, J . Amer . Chem. SOG., 1958, 80, 4466. 478 0. Schmitz-Du Mont, F. Nagel, and W. Schaal, Angew. Chem., 1958, 70, 105. 479 A. W. Adamson, H. Ogata, J . Grossman, and R. Newbury, J . Inorg. Nuclear

480 E. Paglia, At t i Accad. naz. Lincei, Rend. Classe Sci.fis. mat. nut., 1958, 24, 725;

481 B. Martin and G. M. Waind, J., 1958, 4284; Proc. Chem. Soc., 1958, 169; J .

482 W. MacNevin, H. D. McBride, and E. A. Hakkila, Chem. and Ind., 1968, 101. 483 V. V. Lebedinskii and 2. M. Novozhenyuk, Zhur. neorg. Khim. , 1957, 2, 2490;

484 L. M. Venanzi, J . , 1958, 719; J . Inorg. Nuclear Chem., 1958, 8, 137; see also

485 E. C. Lingafelter, Nature, 1958, 182, 1730.

Chem., 1958, 8, 319.

L. Cambi and E. Paglia, J . Inorg. Nuclear Chem., 1958, 8, 249.

Inorg. Nuclear Chem., 1958, 8, 551.

1958, 3, 286.

G. Giacometti, V. Scatturin, and A. Turco, Gazzetta, 1958, 88, 434.

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colour in paramagnetic nickel@) complexes is not indicative of tetrahedra1 co-ordination, as has been suggested.m6 However, the whole question is by no means fully solved. In formazan complexes of the type shown in

(38), there is considerable steric hindrance from Ar' Ar the aryl groups (Ar), which should favour tetra-

/J=N, hedral configuration. However, the compounds Ni C'R are diamagnetic; this has been interpreted in

terms of a distorted planar structure retaining (38) dsP2 bondingm' A structure analysis of single

crystals of the compound Ni(CN),,NH,,$H,O reveals a modified form of the tetragonal planar nickel complex found in the benzene compound Ni(CN),,NH,,C,H,. The layers are staggered so that the projecting ammonia groups of one layer point towards the holes in the square network of its neighbours. Single crystals of the benzene compound in the presence of moisture change to this hydrate structure.&* Ammines of nickel cyanide have been further and additional structural information on the benzene clathrate obtained from magnetic measurements and infrared ~pectra.4~0

Normal o-bonds between palladium and organic groups can be stabilized by appropriate co-ordination ; organopalladium compounds prepared include the complexes (PEt,),PdMe,, (PEt,),PdPh,, and corresponding phenyl- ethynyl and dimethylaminophenyl compounds.491 NNN'N'-Tetramethyl-o- phenylenediamine reacts readily with an aqueous solution of the compound K,PdCl, giving yellow needles of the stable complex C,H4(NMe2),,PdC1, ; corresponding bromo- and iodo-derivatives have been isolated. This is an interesting example of stability produced by chelation where the ligands themselves have poor co-ordinating p0wers.4~~ The ability of dimethyl-o- methylthiophenylarsine (chel) to function as a chelating ligand is demonstrated by the formation of paramagnetic nickel(11) complexes Ni(chel),X, (X = C1, Br, I). Palladium(I1) forms two types, Pd(chel)X, (which are non-electrolytes in nitrobenzene) and Pd(che1) ,X,. The compound [Pd(chel),](ClO,), has the conductivity expected of a bi-univalent electrolyte in nitr~benzene.~~,

There is a well-defined absorption band (at about 2000 cm.-l) in the infrared spectrum of the stable hydrides (PR,),PtHX (R = alkyl and X = halogen or other univalent acid radical) attributable to the Pt-H stretching frequency. The Pt-H bond strength vanes with X to an extent which is related to the trans-effect exerted by X. An impure palladium analogue (PEt,),PdHCl, and a new platinum hydride (PEt,),PtH,Cl,, have been described.494 X-Ray analysis of the compound (Et4N),[Pt2Br6] has con-

R. q N -

N=NH A r "-"' Ar'

486 L. I. Katzin, Nature, 1958, 182, 1013. 487 H. Irving and J. B. Gill, Proc. Chem. Soc., 1958, 168. 468 J. H. Rayner and H. M. Powell, J.. 1958, 3412. 489 E. E. Aynsley and W. A. Campbell, J., 1958, 1723. '90 M. Kondo and M. Kubo, J . Phys. Chem., 1957, 61, 1648; R. S. Drago, J. T.

Kwon, and R. D. Archer, J . Amer. Chem. SOL, 1958, 80, 2667. 491 G. Calvin and G. E. Coates, Chem. and Ind., 1958, 160. 492 F. H. C. Stewart, ibid., p. 264. 493 S. E. Livingstone, J., 1958, 4222. 404 J. Chatt, L. A. Duncanson, and B. L. Shaw, Chem. and Ind., 1958, 869.

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ADDISON AND GREENWOOD: THE TRANSITION ELEMENTS. 165 firmed the existence of a planar bromo-bridged anion [Pt2Br6I2-; dimeric ions also exist in solution.495 The visible and ultraviolet spectra of a series of ions [Pt(NHs),Cl~4_,~]('-2,+ where n = 0-4, have been interpreted in terms of the orbital-energy diagram for d-electrons on the platinous ion.496 Further studies of the N-H stretching bands in the infrared spectra of complexes of the type trans-[L,am MC1J (where L = ligand, am = amine and M = Pd or Pt) give evidence for interaction between the N-H bonds of co-ordinated amines and the non-bonding d-electrons of the metal atoms.497

The Copper Group.-There has been continued interest in binuclear compounds of copper containing Cu-Cu bonds. Magnetic moments smaller than the theoretical value are observed for a series of trico-ordinated copper- (11) complexes (e.g., with Ei-bromo- and 5-nitro-salicylylideneanthranilic acid) which are discussed in terms of the Cu-Cu distance in dimer molecules.4B8 Cupric monochloro- and dichloro-acetates have dimeric molecules in both dioxan solution and the crystal, but dimerization does not occur with the t r ichloroa~etate .~~~ The dark green cupric derivative of diazoaminobenzene is dimeric and diamagnetic in benzene. There is strong evidence that the molecule adopts a configuration (39) similar to that for copper acetate. The diamagnetism arises from direct intramolecular exchange between copper

atoms, supported vertically in contact by four bridging Ph*N,*Ph groups. [The Ph groups are omitted from structure (39) for clarity.] The spin paramagnetism is completely quenched in this compound, in contrast to the partial quenching observed in copper alkanoates.m In the copper-

(39 ) dimethylglyoxime complex the two rings are at an angle of 28", so that the nitrogen

atoms are in a distorted tetrahedron round the copper atom. This is in contrast to the coplanar system given by the nickel, palladium, and platinum complexes. 501

The infrared spectrum of solid anhydrous copper nitrate differs from that for the ionic nitrates [e.g., Cd(NO,),] ; there are strong bands in the regions 1592-1504 cm.-l and 1289-1264 cm.-l, and at 1016 cm.-l which are characteristic of the co-ordinated nitrate group. The vapour spectrum is simpler than that of the solid, and a new band appears a t 1088 cm.-l which is not observed for the solid.502 The techniques used in the manipulation of copper nitrate vapour have now been d e s ~ r i b e d . ~ ~ The monomeric nature of the

N ~ - ~ ~ ~ ~ ~

/ 7 N. J d N ' 7 N-cu.N

495 C. M. Harris, S. E. Livingstone, and N. C. Stephenson, J. , 1958, 3697. J. Chatt, G. A. Gamlen, and L. E. Orgel, J., 1968, 486. J. Chatt, L. A. Duncanson, and L. M. Venanzi, J . Inorg. Nuclear Chem., 1958,

M. Kishita, Y . Muto, and M. Kubo, Austral. J . Chem., 1957, 10, 386; 1958, 11,

40e R. Tsuchida, S. Yamada, and H. Nakamura, Nature, 1958, 181, 479. C. M. Harris and R. L. Martin, Proc. Chem. SOC., 1958, 259.

601 E. Frasson, R. Zannetti, R. Bardi, S. Bezzi, and G. Giacometti, J . Inorg. Nuclear

602 C. C. Addison and B. M. Gatehouse, Chem. and Ind., 1958, 464. C . C. Addison and B. J. Hathaway, J., 1958, 3099; C. C. Addison, B. J. Hatha-

8, 67; J., 1958, 3203.

309.

Chem., 1958, 8, 452.

way, and N. Logan, J . Inovg. Nuclear Chem., 1958, 8. 569.

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vapour has been confirmed from its mass spectrum which also indicates the presence of Cu(NO,)+, CuO+, and Cu+ species formed by dissociative ionization of Cu(NO,),(g) in the ion source.6oQ Unexpected volatility has been found in copper perchlorate also. Nitrosyl perchlorate reacts with copper oxide, cupric chloride, nitrate or perchlorate dihydrate, yielding in a vacuum at 200" a crystalline sublimate Cu(ClO,),-,(NO,),; f i frequently corresponds to unity. Further fractional sublimation yields pure anhydrous copper perchlorate, which is thermally stable to 130" and melts a t 230-240" on rapid heating. Like cupric nitrate the perchlorate is soluble in many oxygen- and nitrogen-containing solvents.rn5 Copper forms azide-complex ions such as Cu,(N,),-, Cu(N,),-, Cu(N,),2-, and Cu(N,),4- which readily decompose in water with separation of the simple azide Cu(N,),. From a spectrophotometric study of copper perchlorate-sodium azide aqueous solutions, the ion Cu(N,)+ has now been identified.m A sodium-gold azide NaAu,.,N,., has been obtained as orange-red needles.507

The structure of thelsoliasilver perchlorate-benzene complex C6H6,AgC104 has been refined. The benzene ring is distorted; the C-C distances nearest the silver ions are 1.35A, whereas the others are 1*43A.508 Tervalent as well as bivalent silver has been formed a t a rotating-disc electrode in alkaline s o l ~ t i o n , ~ ~ and anodic oxidation of silver fluoride and silver nitrate baths also gives an oxide in which the valency of the silver exceeds X-Ray diffraction has confirmed that auric chloride exists in the solid state as planar dimeric molecules Au,Cl,, as in the gas.511

The Zinc Group.-When water vapour is passed over zinc oxide at 1300", the quantity of solid which vaporizes is a linear function of the water-vapour pressure; Zn(OH), is the volatile species.512 The course of autoxidation of alkylcadmium compounds is similar to that of Grignard reagents or alkylboron compounds. Reaction of a cadmium alkyl with an organic hydroperoxide or dissolved oxygen in ether solution gives organo- peroxy-cadmium compounds Cd(0*OR),.513

The infrared spectrum of amidomercurysulphonic acid indicates that it is an inner salt H,N+*Hg*S0,-.514 The compound formed by absorption of ethylene in methanolic mercuric acetate is usually assigned the formula MeOCH,*CH,*Hg*OAc, though evidence for such a structure has been limited. The proton resonance spectrum of this compound, and also of the related compound HO*CH,*CH,*Hg*OH, now provides strong support for these structures.515 The mercury derivative of dithizone has been studied by X-ray diffraction, the red crystals Hg(C13HllN4S)2,2C5H5N, which

504 R. F. Porter, R. C. Schoonmaker, and C. C. Addison, Proc. Chem. SOL, 1959, 11. 605 B. J . Hathaway, ibid., 1958, 344. 506 G. Saini and G. Ostacoli, J. Inorg. Nuclear Chem., 1958, 8, 346. 607 G. T. Rogers, ibid., 1958, 5, 339. 508 H. G. Smith and R. E. Rundle, J . Amer. Chem. SOC., 1958, 80, 5075.

510 W. S. Graff and H. H. Stadelmaier, J. Electrochem. SOC., 1958,105, 446. 611 E. S. Clark, D. H. Templeton, and C. H. MacGillavry, Acta Cryst., 1958, 11, 284. 512 0. Glemser, H. G. Volz, and B. Meyer, 2. anorg. Chem., 1957, 292, 311. 518 A. G. Davies and J. E. Packer, Chern. and Ind. , 1958, 36, 1177. 51p K. Brodersen, Chem. Ber., 1957, 90, 2703. 516 F. A. Cotton and J. R. Leto, J. Amer. Chem. SOC., 1958, 80, 4823.

Yu. V. Pleskov, Doklady Akad. Nauk S.S.S.R. . 1957, 117, 645.

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ADDISON AND GREENWOOD: THE TRANSITION ELEMENTS. 167 crystallize from aqueous pyridine, being used. The primary bonding to mercury is through the sulphur atoms.516 Perfluoro-derivatives of alkyl- mercurials and alkylmercuric halides react with alkali halides to form complex ions. Conductivity measurements indicate the existence of complexes KHg(CF,),X and K,Hg(CFJ,X, (X = halogen) .617

C. C. ADDISON. N. N. GREENWOOD.

516 M. M. Harding, J., 1958, 4136 617 H. J. EmeICus and J. J. Lagowski, Proc. Chem. SOL, 1958, 231.

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inorganic chemistry

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