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

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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

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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

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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

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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-

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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

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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

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