reaction of large-bite ligands with various tellurium compounds: synthesis and structural...

Polyhedron 18 (1999) 2861–2867www.elsevier.nl / locate /poly

Reaction of large-bite ligands with various tellurium compoundsSynthesis and structural characterization of [Te (m-Cl) h(SPPh ) Nj ],2 2 2 2 2

[(4-MeOC H TeCl ) hm-Ph P(S)CH CH P(S)Ph j] and6 4 3 2 2 2 2 2

[Te (m-Ph PS ) ] representing novel types of tellurium complexes2 2 2 2a b a c c¨Josef Novosad , Karl W. Tornroos , Marek Necas , Alexandra M.Z. Slawin , J. Derek Woollins ,

b ,*Steinar Husebyea ´ ´Department of Inorganic Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno, Czech Republic

b ´Department of Chemistry, University of Bergen, Allegaten 41, N-5007 Bergen, NorwaycDepartment of Chemistry, Loughborough University, Loughborough LE11 3TU, UK

Received 30 March 1999; accepted 30 June 1999

Abstract

The three title compounds have been synthesized and their structures determined by X-ray crystallography. [Te (m-Cl) h(SPPh ) Nj ],2 2 2 2 2

1, is a dinuclear square planar Te(II) complex where each Te atom is coordinated to the two sulfur atoms of the bidentate dithiolate ligand˚and to the two bridging chloride ligands. The Te–S bond lengths are 2.4980(8) and 2.5054(8) A, while the Te–Cl bond lengths are

˚2.9065(9) and 2.9230(9) A. In [(4-MeOC H TeCl ) hm-Ph P(S)CH CH P(S)Ph j], 2, the dithio ligand is neutral and adds a molecule of6 4 3 2 2 2 2 2

[4-MeOC H TeCl ] at each sulfur atom, thus bridging the two Te(IV) atoms. The coordination of both tellurium atoms is c-octahedral6 4 3˚with the anisyl group and a lone pair of electrons in axial positions. The Te–S bonds, 2.7747(6) and 2.8198(5) A, are surprisingly weak

˚while the Te–Cl bonds lie in the range 2.4247(5) to 2.5343(6) A, those trans to Te–S being shortest. [Te (m-Ph PS ) ], 3, is a binuclear2 2 2 2˚Te(I) complex, mainly held together by a Te–Te bond of 2.7298(5) A. Both anisobidentate diphenyldithiophosphinate ligands bridge the

two tellurium atoms. The resulting coordination around each tellurium is best described as T-shaped with the Te–Te bond along the stem.˚In the asymmetric near linear S–Te–S system, the short Te–S bonds are 2.487(2) and 2.495(2) A while the long bonds are 2.947(2) and

˚3.033(2) A, respectively. The strongly different trans influences of the dithio ligands of 1 and 2 are discussed and it is suggested that theyare dependent upon the basicity of the sulfur atoms. 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Tellurium complexes; Basicity and trans influence of ligands

1. Introduction Ph P(S)CH P(S)Ph , (L-L)9 [5], should be reduced as2 2 2

electron transfer to the chalcogen atoms no longer takesplace (Scheme 1). The ligand (L-L)9 adds to TeCl to formBidentate dichalcogeno ligands with large bites, (L-L), 4

IVare known to give Te(II) chelates of the type Te(L-L) an octahedral complex, [Te Cl (L-L)9] [6]. There is no2 4

with a square planar structure [1–3]. With ArTeCl they disproportionation with formation of a Te(II) complex in3

react to produce dimeric structures of the type [ArTe(L-L)] with a T-shaped geometry around each Te(II) atom2

[2,4]. In all except one of the complexes above, (L-L)52[Ph P(E)NP(E)Ph ] , where E is S or Se. This type of2 2

anionic ligand is a good nucleophile due to electrontransfer from the central N atom towards the chalcogenatoms. If the N atom is replaced by a methylene group insuch a ligand, the basicity of the resulting neutral ligand,

Scheme 1. Large bite P–N–P and P–C–P ligands in order of decreasing*Corresponding author. Tel.: 147-55-58-3551; fax: 147-55-58-9490. basicity. The ligand (L-L)9 referred to in the text is similar to (L-L)0, butE-mail address: [email protected] (S. Husebye) has only one CH group connecting the two phosphorus atoms.2

0277-5387/99/$ – see front matter 1999 Elsevier Science Ltd. All rights reserved.PI I : S0277-5387( 99 )00195-3

2862 J. Novosad et al. / Polyhedron 18 (1999) 2861 –2867

this case. Such disproportionation is very common for and does not form a simple addition compound like thereactions between Te(IV) compounds and monodentate or ligand [Ph P(S)CH P(S)Ph ], (L-L)9 [6]. Surprisingly it2 2 2

bidentate chalcogeno ligands, except for forms a dinuclear chloro-bridged square planar telluriumdialkyldithiocarbamates [7]. complex rather than a square planar Te(L-L) complex2

As the Te(L-L) complexes had been made by simple (Fig. 1). We believe this is the first, halogen-bridged2IIdisplacement of thiourea (tu) ligands on [Te (tu) ]Cl [8], dinuclear tellurium complex of this type with a TeS Cl4 2 2 2

2we found it worthwhile to test the addition of protonated coordination sphere where both Cl ligands are bridging(L-L) directly to TeCl as the protonated ligand should and the two ligand S atoms belong to the same bidentate,4

have a lower basicity than the corresponding anion. Still chelate ligand. However, polymeric trapezoid planar com-the nucleophilicity is expected to be higher than that of plexes with a TeS X (X5halogen) coordination sphere2 2

(L-L)9 due to partial delocalization of the nitrogen lone are known [11].pair of electrons over the SPNPS system (Scheme 1). We Adding the ligand Ph P(S)(CH ) P(S)Ph , (L-L)0, to2 2 2 2

also wanted to test another related highly nucleophilic 4-MeO-C H TeCl resulted in an addition compound, but6 4 3

ligand, Ph P(S)NC(S)pip (pip5piperidyl) [9] for complex the ligand unexpectedly adds to the tellurium compound in2

formation with tellurium. the ratio 1:2 forming a dinuclear complex [(4-MeO-In addition, we were interested in testing the large-bite C H TeCl ) hm-(L-L)0j], 2, by means of Te–S bonding6 4 3 2

ligand Ph P(S)(CH ) P(S)Ph [10], another weak nu- (Fig. 2). The coordination is c-octahedral with the lone2 2 2 2

cleophile, as to its ability to form addition compounds with pair of electrons on Te(IV) trans to the anisyl group. SuchArTeX (X5halogen) and other tellurium halogenides. a structure has earlier been proposed for the analogous3

The ligands are shown in Scheme 1. complex with the ligand Ph P(Se)CH CH P(Se)Ph [12].2 2 2 2

This is also an unusual type of tellurium structure with alarge bite bidentate bridging ligand. A similar bridgingmode for the dithio ligand is found in the complex

2. Results and discussion[(AlCl ) hm-(L-L)0j], where the ligand bridges the two3 2

aluminium atoms [10].Addition of the protonated ligand H(L-L) to TeCl in4 The reaction between the ligand [Ph P(S)NC(S)pip],2the ratio 1:1 resulted in the dinuclear, centrosymmetric

where pip5piperidyl, and [Te(tu) ]Cl , resulted in split-4 2complex [Te (m-Cl) (L-L) ], 1. This is a Te(II) complex,2 2 2 ting of the ligand and subsequent formation of the complexprobably formed as a result of the following disproportio-

[Te (m-Ph PS ) ], 3, which can be considered built up of2 2 2 2nation: I 21 2a [Te ] part bonded to two Ph PS ligands. The2 2 2

resulting binuclear complex has the same structure as that2TeCl 1 6 H(L-L) 5 [Te (m-Cl) (L-L) ] 1 2(L-L)4 2 2 2 2

found by Haiduc et al. for the corresponding benzene1 6HCl

solvate, [Te (m-Ph PS ) ]?C H [13]. Each tellurium2 2 2 2 6 62 atom in 3 has a T-shaped coordination, being stronglywhere Te(IV) has been reduced to Te(II) and two (L-L)

bonded to one ligand via sulfur, and trans to this bondions have been oxidized to disulphide, (L-L) . Thus the2

weakly bonded to a sulfur atom of the other ligand. Theligand [Ph P(S)NHP(S)Ph ] is deprotonated in the reaction2 2

Fig. 1. The molecular structure of [Te (m-Cl) h(SPPh ) Nj ], 1. Thermal ellipsoids are given at the 50% probability level.2 2 2 2 2

J. Novosad et al. / Polyhedron 18 (1999) 2861 –2867 2863

Fig. 2. The molecular structure of [(4-MeOC H TeCl ) hm-(Ph P(S)CH CH P(S)Ph )j], 2. Thermal ellipsoids are given at the 50% probability level.6 4 3 2 2 2 2 2

last bond is to the second tellurium atom. However, there consisting of Te? ? ?Te bonds only [13]. Recently, theare secondary bonds [14], Te(2)? ? ?S(2)953.521(5) and synthesis of Te X (X5Cl, Br) has been reported [16].2 2

˚S(4)? ? ?Te(1)953.728(5) A, to a neighbouring molecule. However, no structure is reported for these rather unstableThis may be compared to the sum of the respective van der liquids. In comparison, the structures of Se Br and2 2

22˚Waals radii of 3.86 A [15]. Such weak interactions are [SeBr (Se Br )] show that Se(I) in these compounds6 2 2

very common in tellurium compounds [7,11]. The direc- has a distorted, T-shaped three-coordination [17,18], quitetion (Table 2) of these bonds shows a tendency toward similar to that found in 3 (Fig. 3).square planar coordination for both tellurium atoms. Thisbonding repeats itself and connects the molecules into

2.1. Tellurium ligand bondingzigzag chains. Although the solvated complex formedsimilar chains, the intermolecular bonding is different,

In 1, the Te–S bond lengths are nearly identical with˚ ˚Te–S(1) being 2.5054(8) A and Te–S(2) 2.4980(8) A.

These bond lengths are much shorter than those found inthe corresponding Te(L-L) complex where the average2

˚Te–S bond length is 2.687 A [1]. The latter value is˚normal for square planar Te(II)S coordination (2.68 A)4

[7,11]. Bonding in Te(II) and Te(IV) complexes is subjectto trans influences [7,19], and thiolates and thioureas havea greater trans influence than halogens. Thus we shouldexpect a strengthening of the Te–S bonds in 1 at theexpense of the trans situated Te–Cl bonds. Being furtherweakened as a result of bridging, the Te–Cl bond lengths

˚are accordingly found to be Te–Cl, 2.9065(9) A and˚Te–Cl9, 2.9230(9) A. Comparing the sum of the respective˚ ˚covalent radii, 2.41 A for Te–S and 2.36 A for Te–Cl [20],

illustrates these effects. In square planar Te(II) complexeswith cis TeS X coordination spheres where S represents a2 2

monodentate thiourea, the Te–S bonds typically are in the˚range 2.45–2.50 A, whereas Te–Cl bonds are around 2.90

A [7,11]. In 2 with Te(IV) as a central atom, the Te–SFig. 3. The molecular structure of [Te hm-(Ph PS )j ], 3. A neighbour2 2 2 2 bonds are again trans to Te–Cl bonds. However, inmolecule is shown below to illustrate the intermolecular secondary

contrast to what is found for 1, the Te–S bonds are muchbonding. Such interactions also take place on the other side of thelonger and weaker than the trans situated Te–Cl bonds.molecules, thus forming chains. Thermal ellipsoids are given at the 50%

probability level. This implies that the trans influence of the ligand (L-L)0 is


2 ˚smaller than that of Cl . Here Te(1)–S(1)52.7747(6) A found in compounds where the phosphorus atom also is˚and Te(2)–S(2)52.8198(5) A, while Te(1)–Cl(11)5 bonded to three carbons [21]. The complex [(AlCl ) hm-3 2

˚ ˚ (L-L)0j] has a structure similar to that of 2, with P–S bond2.4395(6) A and Te(2)–Cl(21)52.4247(5) A. This sup-˚lengths being 1.989(2) A [10]. In the complexes [Cu (m-ports the idea of a weaker basicity of the neutral lig- 2

Cl) hm-(L-L)0j ] and [HgCl (L-L)0] [24,25] the averageands Ph P(S)(CH ) P(S)Ph as compared to 2 2 22 2 n 22 ˚P–S bond lengths are 1.986 and 1.994 A, respectively. In[Ph P(S)NP(S)Ph ] . The four other Te–Cl bond lengths2 2

˚ ˚ the ligand L-L in 1, the average P–S bond length is aboutrange from 2.4738(6) to 2.5343(4) A (ave. 2.508 A).˚0.05 A longer. This difference in P–S bonding is reflectedThese bond lengths are in the normal range for Te(IV)–Cl

in the Te–S bond lengths in 1 and 2, where the average forbonds and significantly longer than the correspond-˚1 is 0.29 A shorter than that found for 2. In [TeCl (L-L)9]ing bonds trans to the Te–S bonds. A comparison 4

where the ligand (L-L)9 is of the same type as (L-L)0 in 2,with the complex [TeCl hm-(L-L)9j], [(L-L)954

except for having only one central methylene group insteadPh P(S)CH P(S)Ph ], which is octahedral with the two2 2 2˚Te–S bonds trans to Te–Cl bonds, shows that also in this of two, the average P–S value is 1.967 A, even shorter

case the Te–S bonds are weaker than the trans situated than that found in 2 [6]. In comparison, the free ligands˚Te–Cl bonds [2.891(3) and 2.633(4) A for Te–S vs. (L-L)9 and (L-L)0 have average P5S double bond lengths

˚˚ of 1.945 and 1.941 A [5,26]. In the addition compound2.362(4) and 2.386(4) A for Te–Cl] [6]. The Te(1)–C(1)˚ HgPh .(L-L)0 with very weak Hg? ? ?S interactionsand Te(2)–C(8) bond lengths at 2.126(2) and 2.135(2) A 2

˚˚ [3.913(4) A], the P5S bond length is 1.956(2) [27]. Theare close to the standard statistical value of 2.116(20) A˚found for the Te–C bond [21]. P–C (alkyl) bonds have an average value of 1.815 A whilear

˚In 3, the formal oxidation state of tellurium is 11. the central C–C bond is 1.537(3) A; both normal valuesThere are two short Te–S bonds [Te(1)–S(3)52.487(2), [21]. Angles Te(1)–S(1)–P(1) and Te(2)–S(2)–P(2) are

˚Te(2)–S(1)52.495(2) A], each trans to a long Te–S bond 102.96(3) and 108.29(2)8, respectively. This compares to˚[Te(1)–S(2)52.947(2), Te(2)–S(4)53.033(2) A]. These average values of 99.78 and 110.58 for 1 and [TeCl (L-4

values compare well with average short and long bonds in L)9] and reflect the flexible nature of these angles. The2˚the corresponding benzene solvate, 2.482 and 3.028 A diphenyldithiophosphinate ligand, Ph PS , has essentially2 2

˚[13]. The Te(1)–Te(2) bond length is 2.7298(5) A which the same structure in 3 as found in the correspondingis very close to twice the covalent radius of tellurium, 2.74 benzene solvate [13]. For the sulfurs strongly bonded toA [20]. It is also close to the Te–Te bond length in the tellurium, P(1)–S(1)52.065(2) and P(3)–S(3)52.059(2)

˚ ˚benzene solvate, 2.723 A, and in ditellurides [13,22]. Also A, close to that found in 1. For the remaining sulfur atomsthe S–Te–Te angles [Te(1)–Te(2)–S(1)593.26(4) and S(2) and S(4), P(1)–S(2)51.981(2) and P(3)–S(4)5

˚Te(2)–Te(1)–S(3)591.98(4)8] involving the two strongly 1.980(2) A. These shorter bond lengths result from thebonded sulfur atoms S(1) and S(3) lie in the range found weaker Te–S bonding from these sulfur atoms, as com-for the corresponding C–Te–Te angles in ditellurides pared to S(1) and S(3).(85.8–101.78) [22]. In all three compounds, the P–C (aryl) bonds are normal

˚(range 1.800–1.820 A) [21]. Also the two P–C (alkyl)˚bonds in 2 (average 1.815 A) are in the same range.

2.2. Ligands

The bonding and structure of the ligand2 2[Ph P(S)NP(S)Ph ] , (L-L) in 1 is similar to other 3. Experimental2 2

complexes with this ligand [1,2,23]. The P–S bond lengths˚are P(1)–S(1)52.0586(12) and P(2)–S(2)52.0546(11) A, 3.1. General and instrumental

˚while P(1)–N51.594(3) and P(2)–N51.588(2) A, reflect31the delocalized p bonding through the ligand (Scheme 1). The P-NMR spectra were recorded in CH Cl on a2 2

The atoms S(1), S(2), P(1) and P(2) are coplanar; Te is Bruker AVANCE DRX 500 instrument using as external˚ ˚located 1.587(1) A above this plane and N 0.436(3) A ref. H PO (85%). TeCl and solvents were commercial3 4 4

below, thus establishing a chair form of the six-membered products and were used without further purification. Thechelate ring. The central P–N–P angle is normal at starting materials [Te(tu) ]Cl ?2H O, Ph P(S)NHC(S)pip,4 2 2 2

132.5(2)8 and the Te–S–P and S–P–N angles have Ph P(S)NHP(S)Ph and [4-MeOC H TeCl ] were pre-2 2 6 4 3

average values of 99.78 and 116.018. pared according to literature methods [8,9,28,29]. TheThe ligand Ph P(S)(CH ) P(S)Ph , (L-L)0, is neutral ligand Ph P(S)CH CH P(S)Ph was made by a similar2 2 2 2 2 2 2 2

with no p delocalization. This is reflected in the bonding in procedure to that of the analogous ligand with one2. The P(1)–S(1) and P(2)–S(2) bond lengths are methylene group [5]. Microanalysis were performed on a

˚1.9979(7) and 2.0030(7) A, respectively. This is much Fisoin’s EA 1108 instrument at the Palacky University,˚closer to a double bond length, 1.954 (5) A, the average Olomouc, the Czech Republic.


Table 1Crystal data and structure refinement parameters

Empirical formula C H C N P S Te C H C O P S Te C H P S Te48 40 12 2 4 4 2 40 38 16 2 2 2 2 24 20 2 4 2

Formula weight 1223.04 1144.66 753.78Temperature 293(2) K 243(2) K 293(2) KColour Yellow Yellow Red

˚ ˚ ˚Wavelength 0.71073 A 0.71073 A 0.71073 ACrystal system Monoclinic Triclinic Monoclinic

]Space group P2 /c P1 P2 /n1 1

˚ ˚ ˚Unit cell dimensions a59.5923(4) A a59.7779(2) A a518.0553(3) A˚ ˚ ˚b520.1900(9) A b512.2794(3) A b57.03340(10) A˚ ˚ ˚c512.9106(5) A c519.59320(10) A c521.5825(4) A

a 5908 a 591.6460(10)8 a 5908

b 597.9090(10)8 b 596.8030(10)8 b 591.3280(10)8g 5908 g 5102.1500(10)8 g 5908.

3 3 3˚ ˚ ˚Volume 2476.59(18)A 2280.11(7) A 2740.03(8) AZ 2 2 4

3 3 3Density (calculated) 1.640 Mg/m 1.667 Mg/m 1.827 Mg/m21 21 21Absorption coefficient 1.620 mm 1.826 mm 2.563 mm

F(000) 1208 1124 14483 3 3Crystal size 0.2830.1330.08 mm 0.4730.1730.10 mm 0.0530.130.15 mm

Theta range for data coll. 1.89 to 28.298 1.05 to 31.578 1.45 to 23.308

Reflections collected 38954 44515 11310Independent reflections 6142 [R(int)50.0824] 15196 [R(int)50.0441] 3937 [R(int)50.0555]Absorption correction Numerical integration Numerical integration EmpiricalRefinement method Full-matrix least-squares Full-matrix least-squares Full-matrix least-squares

2 2 2on F on F on FData / restraints /parameters 6142/0 /280 15196/0 /489 3887/0 /290

2Goodness-of-fit on F 1.077 1.029 1.026Final R [I . 2sigma(I)] R1 5 0.0384, wR2 5 0.0785 R1 5 0.0281, wR2 5 0.0634 R1 5 0.0326, wR2 5 0.0612R indices (all data) R1 5 0.0626, wR2 5 0.0866 R1 5 0.0398, wR2 5 0.0679 R1 5 0.0596, wR2 5 0.0940

23 23 23˚ ˚ ˚Largest diff.peak and hole 1.011 and 20.734 eA 0.677 and 20.832 eA 0.673 and 20.592eA

31 13.2. Synthesis of [Te (m-Cl) h(SPPh ) Nj ] (1) 5.60%. Found: C 42.09, H 3.23, S 5.13%. P-h Hj NMR2 2 2 2 2

singlet d 545.84 ppm.Anhydrous TeCl (0.539 g; 2 mmol) was dissolved in4

acetonitrile (40 ml) and added by stirring into an acetoni- 3.4. Synthesis of [Te hm-(Ph PS )j ] (3)2 2 2 2

trile solution (40 ml) of Ph P(S)NHP(S)Ph (0.898 g; 22 2

mmol). The mixture was refluxed for 10 s and then A clear solution of [Ph P(S)NHC(S)pip] (0.50 g; 1.432treduced to 50% of its original volume under vacuum. mmol) and KO Bu (0.16 g; 1.43 mmol) in 15 ml methanol

Upon cooling, a solid was formed and then washed by was added to a solution of [Te(tu) ]Cl .2H O (0,77 g; 1.434 2 2

acetonitrile (2310 ml) and air dried. Yield: 0.25 g (61.4% mmol) in 30 ml ethanol and stirred for 30 min at roombased on ligand added) after recrystallization fromCH Cl . M.p.: 140–1428C. Calculated for Table 22 2

Selected bond lengths and angles for 1C H Cl N P S Te : C 47.13, H 3.29, N 2.29, S 10.48%.48 40 2 2 4 4 231 1Found: C 47.46, H 3.33, N 2.42, S 9.97%. P-h Hj NMR: Te–S(1) 2.5054(8) S(1)–Te –S(2) 91.46(3)

Te–S(2) 2.4980(8) S(1)–Te–Cl 88.04(3)singlet d 527.64 ppm.Te–Cl 2.9065(9) S(1)–Te–Cl9 173.11(3)Te–Cl9 2.9230(9) S(2)–Te–Cl 174.69(3)3.3. Synthesis of [(4-MeOC H TeCl ) hm-6 4 3 2 P(1)–S(1) 2.0586(12) S(2)–Te–Cl9 87.03(3)

(Ph P(S)CH CH P(S)Ph )j] (2)2 2 2 2 P(1)–N 1.594(3) Cl–Te–Cl9 92.84(2)P(1)–C(1) 1.809(3) Te–Cl–Te9 87.16(2)P(1)–C(7) 1.803(3) Te–S(1)–P(1) 100.88(4)A mixture of Ph P(S)CH CH P(S)Ph [17] (0.462 g; 12 2 2 2P(2)–S(2) 2.0546(11) Te–S(2)–P(2) 98.67(4)mmol) in toluene (40 ml) and [4-MeOC H TeCl ] (0.6826 4 3P(2)–N 1.588(2) S(1)–P(1)–N 116.49(10)g; 2 mmol) in toluene (30 ml) was refluxed for 10 min andP(2)–C(13) 1.808(3) S(2)–P(2)–N 115.53(11)

subsequently reduced to 50% of its original volume under P(2)–C(19) 1.802(3) P(1)–N–P(2) 132.58(17)vacuum. Upon cooling, a solid formed. This was washed Te–Te9 4.0186(4) S(1)–P(1)–C(1) 111.58(11)

S(1)–P(1)–C(7) 104.09(11)by toluene (235 ml) and air dried. Yield: 0.79 g (69.0%)S(2)–P(2)–C(13) 110.09(11)after recrystallization from CH Cl . M.p.: 136–1378C.2 2S(2)–P(2)–C(19) 104.81(10)Calculated for C H Cl O P S Te : C 41.97, H 3.32, S40 38 6 2 2 2 2


Table 3 Table 4˚ ˚Selected bond lengths (A) and angles (8) for 2 Selected bond lengths (A) and angles (8) for 3

Te(1)–S(1) 2.7747(6) S(1)–Te(1)–Cl(11) 171.95(2) Te(1)–Te(2) 2.7298(5) Te(1)–Te(2)–S(1) 93.26(4)Te(1)–Cl(11) 2.4395(6) S(1)–Te(1)–Cl(12) 90.21(2) Te(1)–S(2) 2.947(2) Te(1)–Te)2–S(4) 83.76(4)Te(1)–Cl(12) 2.5343(6) S(1)–Te(1)–Cl(13) 87.69(2) Te(1)–S(3) 2.487(2) Te(2)–Te(1)–S(2) 84.58(4)Te(1)–Cl(13) 2.4738(6) S(1)–Te(1)–C(1) 81.72(5) Te(2)–S(1) 2.495(2) Te(2)–Te(1)–S(3) 91.98(4)Te(1)–C(1) 2.126(2) Cl(11)–Te(1)–Cl(12) 91.87(2) Te(2)–S(4) 3.033(2) S(2)–Te(1)–S(3) 173.6(1)Te(2)–S(2) 2.8198(5) Cl(11)–Te(1)–Cl(13) 90.09(2) P(1)–S(1) 2.065(2) S(1)–Te(2)–S(4) 175.1(1)Te(2)–Cl(21) 2.4247(5) Cl(11)–Te(1)–C(1) 90.53(5) P(1)–S(2) 1.981(2) Te(1)–S(2)–P(1) 105.8(1)Te(2)–Cl(22) 2.4922(6) Cl(12)–Te(1)–Cl(13) 177.71(2) P(1)–C(1) 1.806(6) Te(2)–S(1)–P(1) 100.1(1)Te(2)–Cl(23) 2.5307(6) Cl(12)–Te(1)–C(1) 89.08(5) P(1)–C(7) 1.810(6) S(1)–P(1)–S(2) 114.9(1)Te(2)–C(8) 2.135(2) Cl(13)–Te(1)–C(1) 89.71(5) P(3)–S(3) 2.059(2) Te(1)–S(3)–P(3) 101.1(1)P(1)–S(1) 1.9979(7) S(2)–Te(2)–Cl(21) 168.80(2) P(3)–S(4) 1.980(2) Te(2)–S(4)–P(3) 104.1(1)P(2)–S(2) 2.0030(7) S(2)–Te(2)–Cl(22) 98.84(2) P(3)–C(13) 1.806(5) S(3)–P(3)–S(4) 114.7(1)P(1)–C(39) 1.810(2) S(2)–Te(2)–Cl(23) 78.21(2) P(3)–C(19) 1.803(6) Te(1)–Te(2)–S(2)9 146.4(1)P(2)–C(40) 1.820(2) S(2)–Te(2)–C(8) 89.95(5) Te(2)–S(2)9 3.521(5) Te(2)9–Te(1)9–S(4) 143.2(1)C(39)–C(40) 1.537(3) Cl(21)–Te(2)–Cl(22) 92.34(2) Te(1)9–S(4) 3.728(5)P(1)–C(15) 1.801(2) Cl(21)–Te(2)–Cl(23) 90.72(2)P(1)–C(21) 1.800(2) Cl(21)–Te(2)–C(8) 91.22(5)P(2)–C(27) 1.739(2) Cl(22)–Te(2)–Cl(23) 173.25(2)P(2)–C(33) 1.810(2) Cl(22)–Te(2)–C(8) 86.54(5) CB2 1EZ, UK on request, quoting the deposition numbers

Cl(23)–Te(2)–C(8) 87.38(5) 117158, 117159 and 117160.Te(1)–S(1)–P(1) 102.96(3)Te(2)–S(2)–P(2) 108.29(2)S(1)–P(1)–C(39) 110.14(7)S(2)–P(2)–C(40) 111.53(7) AcknowledgementsP(1)–C(39)–C(40) 111.5(1)P(2)–C(40)–C(39) 111.0(1) The first author thanks NATO for a grant through the

Norwegian Research Council (Grant No. 126230/410) andthe Grant Agency of the Czech Republic for Grants No.203/97/0955, 203/98/0676 and 203/99/0067. The hos-

temperature. The red precipitate was filtered off, washed pitality of the Department of Chemistry, University ofwith ethanol (2310 ml) and dried under vacuum. Suitable Bergen, Norway is gratefully acknowledged.crystals for X-ray diffraction were obtained by recrystalli-zation from CH Cl /hexane. Yield: 0.33 g (61.2%) after a2 2

primary recrystallization from CH Cl . Mp.: 147–1498C.2 2 References

˚[1] S. Bjørnevag, S. Husebye, K. Maartmann-Moe, Acta Chem. Scand.3.5. Structure determinationA36 (1982) 195.

[2] J. Novosad, S.V. Lindeman, J. Marek, J.D. Woollins, S. Husebye,The X-ray data for 1 and 2 were collected on a Bruker- Heteroatom Chem. 12 (1998) 615.

AXS SMART2K CCD diffractometer, those for 3 were [3] R. Zagler, B. Eisenmann, Z. Naturforsch. 46B (1991) 593.[4] S. Husebye, K. Maartmann-Moe, Ø. Mikalsen, Acta Chem. Scand.collected on a Siemens SMART CCD diffractometer. In

44 (1990) 802.excess of a full sphere of reflections were collected for 1[5] C.J. Carmalt, A.H. Cowley, A. Decken, Y.G. Lawson, N.C. Norman,and 2. For 3, in excess of a full hemisphere was collected.

Acta Crystallogr., Sect. C 52 (1996) 931.The data were collected, reduced and the structures solved [6] C.J. Carmalt, N.C. Norman, L.J. Farrugia, Polyhedron 14 (1995)using the programs SMART, SAINT and SHELXTL 1405.

[7] S. Husebye, in: F.J. Berry, W.R. McWhinnie (Eds.), Proceedings of[30,31]. All non-hydrogen atoms were refined aniso-the Fourth International Conference on the Organic Chemistry oftropically and the hydrogen atoms were given isotropicSelenium and Tellurium, The University of Aston, Birmingham,displacement parameters equal to 1.5 (1,2) and 1.2 (3)UK, 1983, p. 298.

times the equivalent isotropic displacement factor of the [8] O. Foss, S. Hauge, Acta Chem. Scand. 15 (1961) 1616.parent carbon atom. Crystallographic and structure de- [9] A. Ziegler, V.P. Botha, I. Haiduc, Inorg. Chim. Acta 15 (1975) 123.termination data are listed in Table 1. Selected bond [10] M.F. Self, B. Lee, S.A. Sangokoya, W.T. Pennington, G.H. Robin-

son, Polyhedron 9 (1990) 313.distances and angles of 1, 2 and 3 are listed in Tables 2–4.[11] I. Haiduc, R.B. King, M.G. Newton, Chem. Rev. 94 (1994) 301.[12] T.N. Srivastava, J.D. Singh, S.K. Srivastava, Polyhedron 6 (1987)

219.[13] M.G. Newton, R.B. King, I. Haiduc, A. Silvestru, Inorg. Chem. 32Supplementary data

(1993) 3795.[14] N.W. Alcock, Adv. Inorg. Chem. Radiochem. 15 (1972) 1.

Supplementary data are available from the Cambridge [15] A. Bondi, J. Phys. Chem. 68 (1964) 441.Crystallographic Data Centre, 12 Union Road, Cambridge [16] J. Pietikainen, R.S. Laitinen, Chem. Commun. (1998) 2381.


[17] R. Kniep, L. Korte, D. Mootz, Z. Naturforsch. B38 (1983) 1. [26] A.L. Rheingold, G.P.A. Yak, Dept. of Chem., Univ. of Delaware,[18] S. Hauge, V. Janickis, K. Marøy, Acta Chem. Scand. 52 (1998) Newark, DE 19716, USA. Private communication to the Cambridge

1104. Cryst. Database, 1996 (NADXIZ).[19] M.D. Rudd, S.V. Lindeman, S. Husebye, Acta Chem. Scand. 50 [27] T.S. Lobana, M.K. Sandhu, E.R.T. Tiekink, J. Chem. Soc., Dalton

(1996) 759. Trans. (1988) 1401.[20] L. Pauling (Ed.), The Nature of the Chemical Bond, 3rd ed, Cornell [28] R.D. Bereman, F.T. Wang, J. Najdzionek, D.M. Braitsch, J. Am.

University Press, Ithaca, New York, 1960, p. 224. Chem. Soc. 98 (1976) 7266.[21] F.H. Allen, O. Kennard, D.G. Watson, L. Brammer, A.G. Orpen, R. [29] G.T. Morgan, R.E. Kellett, J. Chem. Soc. (1926) 1080.

Taylor, J. Chem. Soc., Perkin Trans. II 1987, S1. [30] Bruker-AXS, SMART and SAINT. Area Detector Control and¨ ¨[22] E.S. Lang, C. Maichle-Mossmer, J. Strahle, Z. Anorg. Allg. Chem. Integration Software, Bruker Analytical X-ray Systems, Madison,

620 (1994) 1678. WI, 1998.[23] J.D. Woollins, J. Chem. Soc., Dalton Trans. (1996) 2893. [31] Bruker-AXS, SHELXTL version 5.10, Bruker Analytical X-ray[24] K.L. Brown, Acta Crystallogr. Sect. B 35 (1979) 462. Systems, Madison, WI, 1998.[25] T.S. Lobana, M.K. Sandhu, N.J. Liddell, E.R.T. Tiekink, J. Chem

Soc., Dalton Trans. (1990) 691.

reaction of large-bite ligands with various tellurium compounds: synthesis and structural...

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