Gmelin Handbook 01 Inorganic Chemistry
8th Edition
Gmelin Handbook of Inorganic Chemistry
8th Edition
Gmelin Handbuch der Anorganischen Chemie
Prepared and issued by
Founded by
8th Edition
Continued by
Achte, völlig neu bearbeitete Auflage
Gmelin-Institut für Anorganische Chemie der Max-Planck-Gesellschaft zur Förderung der Wissenschaften
Director: Ekkehard Fluck
Leopold Gmelin
8th Edition begun under the auspices of the Deutsche Chemische Gesellschaft by R. J. Meyer
E. H. E. Pietsch and A. Kotowski, and by Margot Becke-Goehring
Springer-Verlag Berlin Heidelberg GmbH 1990
Gmelin-Institut für Anorganische Chemie der Max-Planck-Gesellschaft zur Förderung der Wissenschaften
ADVISORY BOARD
Dr. G. Breil, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke (PhilippsUniversität, Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr. H. Grünewald (Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, Frankfurt/Main-Höchst), Prof. Dr. H. Nöth (Universität München), Prof. Dr. H. Offermanns (Degussa AG, Frankfurt/Main), Prof. Dr. G. zu Putlitz (Universität Heidelberg), Prof. Dr. A. Rabenau (Max-Planck-Institut für Festkörperforschung, Stuttgart), Prof. Dr. A. Simon (Max-Planck-Institut für Festkörperforschung, Stuttgart), Prof. Dr. Dr. A. H. Staab (Präsident der Max-Planck-Gesellschaft, München), Prof. Dr. Dr. h.c. mult. G. Wilke (Max-Planck-Institut für Kohlenforschung, Mülheim/Ruhr)
DIRECTOR DEPUTY DIRECTOR
Prof. Dr. Dr. h.c. Ekkehard F1uck Dr. W. Lippert
CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. B. Baker, Dr. P. L. Bayless, Dr. V. Haase, Dr. E. F. Hockings, Dipl.-Ing. G. Kirschstein, Dr. W. F. McNamara, Dr. K. Rumpf
E~ERITUS MEMBER OF THE INsmUTE Prof. Dr. Dr. E. h. Margot Becke
CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
GMELIN HANDBOOK
CHIEF EDITORS
Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. Füssel, H. Hartwig, Dr. H. Katscher, Dr. R. Keim, Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. Krüerke, Dr. P. Me riet , Dr. E. Schleitzer-Rust, Dr. F. A. Schröder, Dr. A. Slawisch, Dr. W. Töpper
STAFF
Dr. G. Bär, D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, D. Benzaid, Dr. L. Berg, G. Börgerding, Dr. R. Bohrer, K. D. Bonn, P. Born-Heck, Dipl.-Ing. V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, Dipl.-Geol. R. Ditz, R. Dowideit, Dipl.-Chem. M. Drößmar, U. Duggen, Dr. H.-J. Fachmann, Dr. J. Faust, B. Fischer, G. Funk, Dipl.-Ing. N. Gagei, Dr. D. Germeshausen, Dr. U. W. Gerwarth, Dipl.-Phys. D. Gras, Dipl.-Bibl. W. Grieser, Dr. I. Haas, R. Hanz, Dr. R. Haubold, B. Heibel, Dipl.-Min. H. Hein, A. Heise-Schuster, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. R. Heumüller, Dr. G. Hönes, Dr. W. Hoftmann, G. Horndasch, Dr. W. Huisl, B. Jaeger, Dr. R. Jotter, Dr. J. von Jouanne, Dr. B. Kalbskopf, Dipl.-Chem. W. Karl, H.-G. Karrenberg, Dipl.-Phys. H. Keller-Rudek, B. Kirchner, P. Klauck, Dipl.-Chem. C. Koeppel, R. Kolb, Dr. M. Kotowski, E. Kranz, Dipl.-Chem. I. Kreuzbichler, Dr. A. Kubny, Dr. W. Kurtz, M. Langer, Dr. B. Ledüc, Dr. A. Leonard, H. Mathis, E. Meinhard, M. Meßer, C. Metz, K. Meyer, Dr. M. Mirbach, Dipl.-Chem. B. Mohsin, Dr. U. Neu-Becker, K. Nöring, Dipl.-Min. U. Nohl, Dr. U. Ohms-Bredemann, Prof. Dr. W. Petz, I. Rangnow, Dipl.-Phys. H.-J. RichterDitten, E. Rieth, E. Rudolph, G. Rudolph, Dipl.-Chem. S. Ruprecht, Dr. B. Sarbas, Dr. H. Schäfer, Dr. R. Schemm, Dr. D. SChiöberg, P. Schleimer, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min. P. Schubert, A. Schwärzei, Dr. B. Schwager, Dipl.-Ing. H. M. Somer, Dr. C. Strametz, G. Strauss, Dr. G. Swoboda, Dr. U. Taubald, M. Teichmann, Dr. D. Tille, Dipl.-Chem. P. Velic, Dipl.-Ing. U. Vetter, H.-M. Wagner, Dipl.-Phys. J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. C. Weber, Dr. A. Wietelmann, Dr. M. Winter, Dr. B. Wöbke, K. Wolft
GMELIN ONLINE
EXEcunvE MANAGER HEAD OF DEPARTMENT
Dr. R. Deplanque Dr. P. Kuhn, Dr. G. OIbrich
STAFF
Dr. R. Baier, Dr. B. Becker, Dipl.-Chem. E. Best, Dipl.-Phys. R. Bost, Dr. A. Brandl, Dr. R. Braun, Dipl.-Chem. R. Durban, Dr. A. Kirchhoft, Dipl.-Chem. H. Köttelwesch, W. Korba, Dr. M. Kunz, Dr. A. Nebel, Dipl.-Chem. R. Nohl, Dr. B. Rempfer, Dr. K. Schücke, U. TÖlle, Dipl.-Ing. H. Vanecek
Volumes published on "Molybdenum" (Syst. No. 53)
* MoLybdenum
Main Volume - 1935
MoLybdenum SuppL. VoL. A 1
Meta!. Technology - 1977
MoLybdenum Suppl Vol A 2a
Element. Physical Properties, Pt. 1 - 1985
MoLybdenum SuppL. Vol A 2b
Physical Properties, Pt. 2. ELectrochemistry - 1988
MoLybdenum SuppL. Vol A 3
Meta!. Chemical Reactions - 1983
MoLybdenum SuppL. VoL. B 1
Compounds with Noble Gases, Hydrogen, and Oxygen. Anhydrous Antimony, Bismuth, and Alkali Molybdates - 1975
MoLybdenum Suppl Vol B 2
Anhydrous Compounds of Molybdenum Oxides with Oxides of Other Metals - 1976
MoLybdenum SuppL. VoL. B 3 a
Oxide Hydrates. MOlybdate Ions - 1987
MoLybdenum Suppl Vol B 3 b
Molybdate and Peroxomolybdate Ions - 1989
MoLybdenum SuppL. VoL. B 4
Hydrous Molybdates of Groups VA to VI B Metals (System Nos. 18 to 52) - 1985
MoLybdenum SuppL. VoL. B 5
Compounds with N, F, Cl - 1990 (present volume)
* in German
in German, with English reviews and marginalia
Gmelin Handbook of Inorganic Chemistry
AUTHORS
EDITORS
CHIEF EDITOR
8th Edition
Mo Molybdenum Supplement Volume B 5
With 75 illustrations
Compounds with N, F, Cl
Hermann Jehn, Forschungsinstitut für Edelmetalle und Metallchemie, Schwäbisch Gmünd
Wolfgang Kurtz, Dietrich Schneider, Ursula Trobisch, Joachim Wagner, Gmelin-Institut, Frankfurt am Main
Hartmut Katscher, Wolfgang Kurtz, Friedrich Schröder
Hartmut Katscher
System Number 53
Springer-Verlag Berlin Heidelberg GmbH 1990
LITERATURE CLOSING DATE: MID OF 1987
IN MANY CASES MORE RECENT DATA HAVE BEEN CONSIDERED
Library 01 Congress Catalog Card Number: Agr 25-1383
ISBN 978-3-662-06329-3 ISBN 978-3-662-06327-9 (eBook) DOI 10.1007/978-3-662-06327-9
This work is subject to copyright. All rights are reserved, whetherthe whole or part 01 the material is concerned, specilically those 01 translation, reprinting, reuse 01 iUustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 01 the German Copyright law where copies are made lor other than private use, a lee is payable to "Verwertungsgesellschaft Wort", Munieh.
© by Springer-Verlag Berlin Heidelberg 1989 Originally pubHshed by Springer-Verlag BerHn Heidelberg New York in 1989. Softcover reprint of the hardcover 8th edition 1989
The use 01 registered names, trademarks, etc., in this publication does not imply, even in the absence 01 a specilic statement, that such names are exempt Irom the relevant protective laws and regulations and therelore Iree lor general use.
Preface
In the first part of this volume the nitrogen-containing compounds of molybdenum are described. The Mo-N system shows that M02N and MoN are the stable nitrides. MOlybdenum metal dissolves nitrogen to some extent but only at high temperatures. To get better insight into the reactions between nitrogen and molybdenum, the solubility, diffusion, adsorption and desorption phenomena, and ion bombardment are included in the section of the Mo-N system. M02N has a large range of homogeneity toward lower nitrogen concentrations. The black hexagonal MoN has only a narrow range of homogeneity. In addition some molybdenum compounds containing nitrogen and oxygen are known.
The second part contains a full description of the compounds of molybdenum with fluorine. The fluorides MoF n with n ~ 2 are metastable while those with n = 3 to 6 are stable and have been observed in the Mo-F system. Pure MoF3 can exist without traces of oxygen, in co nt rast to earlier assumptions. MoF4 was unambigously prepared and characterized in 1957. Its crystal structure is still unknown. MoFs is often contaminated with the oxide fluoride MoOF4 and it is difficult to remove. Even sm all amounts affect the properties of MoFs. MoF6 , which is liquid at room temperature and solidifies to a "plastic" crystal modification below ca. 17SC, is the most investigated of all the molybdenum fluorides. Studies of the physical and chemical properties of all the fluorides MoF3 to MoF6 are complicated by their high sensitivity to traces of water resulting in the formation of oxide fluorides. These are described in aseparate section. Little work has been done on the lower ones, MoOF· 3 H20 to MoOF3 · 0.5 H20, but those of Mov" MoOF4 and Mo02F2, are the most studied transition metal oxide fluorides. MoOF4 forms addition compounds with KrF2 and XeF2. A great variety of oxofluoromolybdate(V) and -(VI) and oxoperoxofluoromolybdate(VI) anions exist in salts of inorganic and organic cations.
In the third part of the volume the molybdenum chlorides are described. MoCl is known only in the gaseous state. The best investigated molybdenum(lI) chloride modification, u"MoCl2, contains the [M06Cls] cluster and is usually designated as M06Cl,2. This cluster has also been found in the structure of (H30h[(M06Cls)Cls]·6H20.ln addition to the stoichiometric u-MoCl3,
there are various nonstoichiometric chlorides ranging from MoCl2.9 to MoCl3.3 . The black MOC4 possibly exists in three crystallographic modifications. MoCls, which is very sensitive to air and moisture, has been investigated the most of all the molybdenum chlorides. The existence of MoCls is still uncertain. Molybdenum chlorine compounds containing additional elements will be described in the following volume.
Frankfurt am Main, October 1989 Hartrnut Katscher
XI
Tabte 01 Contents
Page
1 Molybdenum and Nitrogen .............................................. .
1.1 The Molybdenum-Nitrogen System ..................................... .
1.1.1 The Phase Diagram .................................................. .
1.1.2 Solubility ........................................................... 4
Solubility in Solid Mo (Cl Solid Solution) .......... ,........................... 4 Formation of Cl Solid Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Solubility Limit of the Cl Solid Solution, Solidus Line .......................... 4 Equilibrium Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Thermodynamic Data ................................................... 9 Properties ............................................................. 10 Ageing Behavior ....................................................... 11
Liquid Mo-N Solution ..................................................... 12 Liquidus Line ............... ;.......................................... 12 SOlubility, Equilibrium Pressure, and Thermodynamic Data . . .. .. . .. .. . . . .. . .. . 12
1.1.3 Reaction Kinetics .................................................... 14
Molybdenum-Nitrogen Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Nitride Formation ........................................................ 15
1.1.4 Diffusion, Permeation ................................................. 15
1.1.5 Adsorption .......................................................... 18
Amount of Adsorbed Nitrogen .............................................. 18 Pure Nitrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 Coadsorption with Other Gases ........................... . . . . . . . . . . . . . . . . 22
Heat of Adsorption and Desorption Energy ................................... 23 Kinetics .................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Adsorption Kinetics ..................................................... 24 Thermal Desorption .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Surface Diffusion ........................................................ 28 Physical Properties ....................................................... 28 Special Investigations ..................................................... 29 Adsorption of N-Containing Gases .......................................... 31
1.1.6 Ion Bombardment .................................................... 32
Nitrogen Solution and Nitride Formation ..................................... 32 Nitrogen-Vacancy Interactions ............................................. 35
1.2 Molybdenum Nitrides .................................................. 36
1.2.1 Dimolybdenum Nitride Mo2N ........................................... 36
Homogeneity Range ...................................................... 36 Preparation and Formation ................................................ 37 Crystallographic Properties ................................................ 40 Physical Properties ....................................................... 42 Chemical Reactions ...................................................... 45
Gmelin Handbook Mo Suppl. Vol. B 5
XII
Page
1.2.2 Molybdenum Nitride MoN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Homogeneity Range ...................................................... 46 Preparation and Formation ................................................ 46 The Moleeule ............................................................ 48 Crystallographic Properties ................................................ 48 Physical Properties ....................................................... 50 Chemical Reactions ...................................................... 52
1.2.3 Other Nitrides and Mo-N Alloys .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
1.2.4 Thin Films .......................................................... 53
1.3 Compounds of Molybdenum with Nitrogen and Oxygen ..................... 64
1.3.1 MOOxNy (x=l, y=l) .................................................. 64
1.3.2 Mo02(NH2)2 ......................................................... 64
1.3.3 Mo02(N03)2, M002(N03)~-n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
66
2 Molybdenum and Fluorine ............................................... 67
2.1 The Molybdenum-Fluorine System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.2 Molybdenum Fluorides ................................. . . . . . . . . . . . . . . . . 69
2.2.1 MOlybdenum Fluorides MoF n with n ~ 1 .................................. 69
2.2.2 Molybdenum(l) Fluoride MoF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.2.3 Molybdenum(lI) Fluoride MoF2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.2.4 Molybdenum(lII) Fluoride MoF3 ......................................... 73
Preparation. Formation ................................................... 74 The Moleeules MoF3 and Mo2Fs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 Crystallographic Properties ................................................ 77 Physical Properties ....................................................... 78 Chemical Reactions. Solubility ............................................. 82
2.2.5 Molybdenum(lV) Fluoride MoF4 . • • • • . . . . . • • . . . . . . . . . • • . . . . . . • . • • . . . . . . . • 86
Preparation. Formation ................................................... 86 The Moleeule ............................................................ 88 Crystallographic Properties ................................................ 89 Physical Properties ....................................................... 89 Chemical Reactions. Solubility ............................................. 91
2.2.6 "Mo2Fg" .....•.•••...•••••..••....•..•.......•....................•. 93
2.2.7 Molybdenum(V) Fluoride MoFs ......................................... 94
Preparation. Formation ................................................... 94 The Moleeules ........................................................... 97 Crystallographic Properties ................................................ 101 Mechanical and Thermal Properties ......................................... 103
Density ............................................................... 103
Gmelin Handbook Mo Suppl. Vol. B 5
XIII
Page
Thermal Properties ..................................................... 103 Melting. Boiling. Vaporization .......................................... 103 Thermodynamic Data ................................................. 106
Electrical and Magnetic Properties .......................................... 107 Optical Properties ........................................................ 109
Color. Refractive Index. Electronic Spectra ................................. 109 Vibrational Spectra ..................................................... 110
Chemical Reactions ...................................................... 112 Solubility. Solutions ...................................................... 116
2.2.8 Molybdenum(VI) Fluoride MoF6 •• . . • . • . . . . . • . • • . . . . . . . • . . . . . . • . . . . . . . . . . 117
Preparation. Formation. Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 The Molecule ............................................................ 122
Point Group ........................................................... 122 Electronic Structure .................................................... 122 lonization Potentials Ei' Photoelectron Spectrum ............................ 124 Electron Affinity A ...................................................... 125 Nuclear Magnetic Resonance (NMR). Nuclear Spin-Rotation Interaction ......... 127 Electrical Multipole Moments of the Molecule ............................... 131 Rotational Constant B. Centrifugal Distortion Constants ...................... 131 Atomic Distances r. Inertial Defect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132 Fundamental Vibrations Vi' Vibrational Amplitudes.
Coriolis Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133 Vibrational Relaxation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138 Force Constants ....................................................... 138 Bond Dissociation Energy D(FsMo--F) and Average Bond Energy . . . . . . . . . . . . . . . . 141 Intermolecular Potential ................................................. 141 Mass Spectra .......................................................... 142
Crystallographic Properties ................................................ 143 Mechanical and Thermal Properties ......................................... 146
Mechanical Properties .................................................. 146 Thermal Properties ..................................................... 149 Thermodynamic Data ................................................... 153
Electrical and Magnetic Properties .......................................... 156 Optical Properties ........................................................ 156
Color ................................................................. 156 Raman Spectrum ....................................................... 157 IR Spectrum ........................................................... 158 UV Spectrum .......................................................... 160
Electrochemical Behavior ................................................. 162 Chemical Reactions ...................................................... 162
Handling and Storage ................................................... 163 Physical Changes ...................................................... 164 Reactions with Nonmetallic Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166 Reactions with Metals ................................................... 168 Reactions with Inorganic Compounds ..................................... 170 Reactions with Elements and Inorganic Compounds in Nonaqueous Solutions . . . . 175 Reactions with Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
Solubility. Solutions ...................................................... 181
Gmelin Handbook Mo SuppL VoL B 5
XIV
Page
2.2.9 Molybdenum Fluoride Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
MOmF~+ Cations .......................................................... 183 MoF~ 103)- Anions, n = 4 to 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
2.3 Compounds of Molybdenum with Fluorine and Xenon . . . . . . . . . . . . . . . . . . . . . . . 188
2.4 Compounds 01 Molybdenum with Fluorine and Oxygen . . . . . . . . . . . . . . . . . . . . . . 189
2.4.1 Molybdenum Oxide Fluorides .......................................... 189
MoOF·3H20 ............................................................ 189 MoOF2 •• ,."."""" •• , •• "" •• " •. ,.,.".", ... "" .•.•••• " .... ,.... 190 MoOF2 ,H20 .. "."" .. "" ...... , .. ", .. , .... "" .. ".,., ... ,." ..... ", 190 MoOF3 ,., ...... , •..... ,." .. ,.",.,." .. ,., •.. ".,.,."., .. , ... "...... 191 MoOF3 'O,5H20 .,.,., .... "", .... " ... ,' .. , ...... ", .. , ... ,." ... ",.... 192 Mo03_ xF x' x = 0,2 to 0.97 , , . , ... , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 MoOF4 •••••.•••••.•.•••••• ,............................................ 194
Preparation. Formation .................................................. 194 Moleeules ................. ,........................................... 196 Crystallographic Properties .............................................. 198 Other Physical Properties .................. ,............. . . . . . . . . . . . . . . . . 199 Electrochemical Behavior ......................... , . . . . . . . . . . . . . . . . . . . . .. 202 Chemical Reactions .................................................... 202 Solutions ............................................................. 205
The MoFs-Mo03-HF-H20 System ........................................... 206 MoOF4 ,nH20, n=2, 2.5 ............. ,..................................... 207 MoO(OH)F3 • H20 ......................................................... 208 Mo02F2 .•.•.•••.••.... , •••••.•• ,........................................ 208
Preparation. Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 208 Physical Properties .......... ,.......................................... 209 Chemical Reactions. SOlubility. Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 210
Mo02F2 ·2H20 ........................................................... 211 H3M040 13F .............................................................. 212
2.4.2 Molybdenum Oxide Fluoride Ions ....................................... 212
The Cations MoOF~ (m =1 to 4), M002F~ (n =1,2), and M020 3Ft ................. 212 Oxofluoromolybdate Anions ............................................... 213
Oxofluoromolybdate(lV) ................................................. 213 Oxofluoromolybdates(V) ................................................. 214 Oxofluoromolybdates(VI) ................................................ 220
Oxoperoxofluoromolybdate(VI) Ions ......................................... 233
2.5 Compounds of Molybdenum with Auorine, Oxygen, and Noble Gases ......... 238
2.5.1 KrF2·nMoOF4, n=1 to 3 ............................................... 238
2.5.2 XeF2 ·nMoOF4, n=1 t04 ............................................... 239
2.6 Compounds 01 Molybdenum Containing Fluorine and Nitrogen .. . . . . . . . . . . . .. 243
243
Gmelin Handbook Mo Suppl. Vol. B 5
xv
Page
3 Molybdenum and Chlorine ............................................... 244
3.1 The Molybdenum-Chlorine System. .. . ... . . .. . . .. . . . . . . .. .. . . .... . . . . . ... 244
3.2 Molybdenum Chlorides ................................................ 249
3.2.1 Molybdenum Monochloride MoCl and the MoCI+ Ion ....................... 249
3.2.2 Molybdenum(lI) Chlorides MosCl12 and MoCl2 ..•••••...••..•....••........ 250
Preparation and Formation ................................................ 250 Crystallographic Properties ................................................ 254 Mechanical and Thermal Properties ......................................... 257 Magnetic and Optical Properties ................................ . . . . . . . . . . .. 259 Electrochemical Behavior ................................................. 262 Chemical Reactions ...................................................... 262
Thermal Decomposition, Mass Spectrum, and Action of y Rays . . . . . . . . . . . . . . . .. 262 Reactions with Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 263 Reactions with Inorganic Compounds ..................................... 264 Reactions with Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 266
Solubility ............................................................... 268 Solutions of Molybdenum(lI) Chloride. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 268
3.2.3 MosCl12 ·2Hp
3.2.4 MosCl12 '8 H20
270
271
3.2.5 (H30)2[(MosCla)Clsl' 6 H20 .............................................. 272
3.2.6 MosCl15 ....•••••..•.••..•....••..••.•....••......•••................ 276
3.2.7 Chloromolybdate(lI) Ions .............................................. 276
3.2.8 Molybdenum{lII) Chloride MoCl3 ("u-MoCl3") .............. . . . . . . . . . . . . . . .. 281
Preparation and Formation ................................................ 281 Preparation. Purification. Single Crystals ................................... 281 Formation ............................................................. 283
Crystallographic Properties ................................................ 286 Mechanical and Thermal Properties ......................................... 288 Magnetic and Optical Properties .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 291 Electrochemical Behavior ................................................. 292 Chemical Reactions ...................................................... 292
Stability. Thermal Disproportionation ...................................... 292 Reactions with Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 294 Reactions with Inorganic Compounds ..................................... 295 Reactions with Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 297
Solubility ............................................................... 298
3.2.9 MoCls' 3 H20 ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 299
3.2.10 MoCl3.08 ("ß-MoCl3") ••.•.•••••.••••.•••••.••..•••••••.••.•••••.•••.•. 299
3.2.11 Other Nonstoichiometric Molybdenum(III) Chlorides (MoCl2.9, MoCls.1, and MoCI3.3) ...•..•.....•.•.••.............•..•.....• 300
3.2.12 Chloromolybdate(III) Ions Including Mo2CLä-
Gmelin Handbook Mo Suppl. Vol. B 5
301
XVI
Page
3.2.13 Molybdenum(IV) Chloride MoCl4 ••......•...•......•................... 308
Preparation and Formation ................................................ 309 Preparation ........................................................... 309 Formation ............................................................. 310
The Molecule ............................................................ 313 Crystallographic Properties ................................................ 313 Mechanical and Thermal Properties ......................................... 315 Magnetic and Optical Properties ............................ . . . . . . . . . . . . . . .. 319 Electrochemical Behavior ................................................. 320 Chemical Reactions ...................................................... 320
Stability. Thermal Decomposition. Mass Spectrum ........................... 320 Reactions with Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 322 Reactions with Inorganic and Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .. 323
Solubility ............................................................... 325 Solutions of MoCl4 .............•....................•.................... 325
3.2.14 The MoC~- Ion ..................................................... 326
3.2.15 Molybdenum(V) Chloride MoC~ ....................................... 327
Preparation and Formation ................................................ 327 Preparation ........................................................... 327 Purification .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329 Formation ............................................................. 330
The Molecule ............................................................ 333 Crystallographic Properties ................................................ 335 Mechanical Properties .................................................... 337 Thermal Properties ....................................................... 337 Magnetic and Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341 Electrochemical Behavior ................................................. 344 Chemical Reactions ...................................................... 344
Stability and Decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 344 Reactions with Elements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 347
With Hydrogen ....................................................... 347 With Other Nonmetallic Elements (0, N, Cl, S, C, P) ......................... 349 With Metals .......................................................... 351
Reactions with Inorganic Compounds ..................................... 353 With Water, Hydrogen Peroxide, Ammonia, Nitrogen Oxide,
Hydrogen Halogenides, and Nitrogen-Halogen Compounds ................ 353 With Nonmetallic Sulfur, Selenium, Boron, Carbon, Silicon,
Phosphorus, Arsenic, and Antimony Compounds . . . . . . . . . . . . . . . . . . . . . . . .. 356 With Salts of Alkali Metals, Ammonium or Substituted Ammonium,
and Alkaline Earth Metals ............................................ 359 With SaUs and Oxides of Group 11 to Group V Metals
(Gmelin System Numbers 32 to 50) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 361 With Molybdenum Compounds ......................................... 363 With Salts and Oxides of Subgroups VI to VIII and I Metals
(Gmelin System Numbers 54 to 70) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 366 Reactions with Organic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 369
With Hydrocarbons ................................................... 369 With Alcohols and Other C-, H-, and O-Containing Compounds ............... 371
Gmelin Handbook Mo Suppl. Vol. B 5
XVII
Page
With Organic Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 373 With Organic Halogen Compounds ...................................... 375 With Organic Sulfur, 80ron, and Silicon Compounds ....................... 377 With Organic Phosphorus and Arsenic Compounds ........................ 378
Reactions with Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380 Solubility. Thermodynamic Data and Kinetics of Dissolution ................... 383
Solutions of MoCl5 ...•.....••••••....•..•...•.•...••............•........ 385
3.2.16 Molybdenum(VI) Chloride MoCls ....................................... 386
Physical Constants and Conversion Factors ................................... 390
Gmelin Handbook Mo Suppt. Val. 85