Inorganic Reactions and Methods: The Formation of Bonds to Halogens (Part 2), Volume 4

669 Pages·1990·144.789 MB·English

Inorganic Reacti ons
and Methods
Volume 4
Inorganic Reactions
and Methods
Edltor
Professor A.P. Hagen
Department of Chemistry
The University of Oklahoma
Norman, Oklahoma 73019
Editorial Advisory Board
Professor N. Bartlett Professor A.G. MacDiarmid
Department of Chemistry Department of chemistry
University of California at Berkeley University of Pennsylvania
Berkeley, California 94720 Philadelphia, Pennsylvania 1917 4
Professor M. Schmidt
Professor F.A. Cotton
lnstitut fur Anorganische Chemie der
Department of Chemistry
Universitat
Texas A&M University
D-8700 Wurzburg
College Station, Texas 77840
Am Hubland
Federal Republic of Germany
Professor E.O. Fischer
Anorganisch-chemisches Laboratorium Professor H. Taube
der Technischen Universitat Department of Chemistry
D-8046 Garching Stanford University
Lichtenbergestrasse 4 Stanford, California 94305
Federal Republic of Germany
Professor L.M. Venanzi
Professor P. Hagenmuller Laboratorium fur Anorganische Chemie
Laboratoire de Chemie du Solide du der ETH
C.N.R.S. CH-80006 Zurich
351 cours de ia Liberation Universitatsstrasse 5
F-33405 Talence Switzerland
France
Professor Sir Geoffrey Wilkinson, F.R.S.
Professor M.F. Lappert Department of Chemistry
The Chemical Laboratory Imperial College
University of Sussex South Kensington
Falmer, Brighton, BN1 9A3 London, SW7 2AY
England England
0 I991 VCH Publishers, Inc., New York
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In o rga n ic React ions
and Methods
Volume 4
The Formation of Bonds to
Halogens (Part 2)
~
Founding Editor
J.J. Zuckerman
Editor
A.P. Hagen
@3 WILEY-VCH
Library of Congress Cataloging-in-Publication Data
Inorganic reactions and methods.
Includes bibliographies and indexes.
Contents: v. 1. The formation of bonds to hydrogen -
pt. v. The formation of the bond to hydrogen -
2, 2.
v. 15. Electron-transfer and electrochemical
reactions; photochemical and other energized reactions.
1. Chemical reaction, Conditions and laws of -
Collected works. Chemistry, Inorganic - Synthesis -
2.
Collected works. I. Zuckerman, Jerry J.
QD501.1623 1987 541.3’98 5-15 627
(set)
ISBN 0-89573-250-0
0 1991 VCH Publishers, Inc.
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ISBN 0-471-18657-0
ISBN 3-527-26275-X VCH Verlagsgesellschaft
Contents of Volume 4
How to Use this Book
Preface to the Series
Editorial Consultants to the Series
Contributors to Volume 4
2.0 The Formation of Bonds to Halogens
(Part 2)
2.6 The Formation of the Halogen-Group-
IllB Element (B, Al, Ga, In, TI) Bond
2.6.1. Int rod uction.
2.6.2. from the Elements.
2.6.3. by Halogenation of the Elements.
2.6.3.1. with Hydrogen Halides.
2.6.3.2. with Carbon-Halogen Compounds.
2.6.3.3. with Other Halides.
2.6.4. from Halogenation of Anionic Group-IIIB
Clusters. 7
2.6.4.1. by Elemental Halogens. 7
2.6.4.2. by Other Halides. 9
2.6.5. from Cleavage of Group-IIIB-Hydrogen
Bonds. 10
2.6.5.1. by Halogens. 10
2.6.5.2. by Hydrogen Halides. 13
2.6.5.3. with Other Halides. 14
2.6.6. from Cleavage of Group-IIIB-Oxygen
Bonds. 16
2.6.6.1. by Halogens. 16
2.6.6.2. by Halogens with Reducing Agents. 17
2.6.6.3. with Hydrogen Halides. 18
2.6.6.4. by Other Halides. 19
2.6.7. from Cleavage of Group-IIIB-Other
Gr oup -VI Element Bonds. 21
B
2.6.7.1. by Halogens. 22
V
vi Contents of Volume 4
2.6.7.2. by Hydrogen Halides. 23
2.6.7.3. by Other Halides. 24
2.6.8. from Cleavage of Group-IIIB-Nitrogen
Bonds. 28
2.6.8.1. by Halogens. 28
2.6.8.2. with Hydrogen Halides. 29
2.6.8.3. with Other Halides. 31
2.6.9. from Cleavage of the Group-IIIB-Other
Group-VB Element Bond. 33
2.6.9.1. by Halogens. 33
2.6.9.2. by Hydrogen Halides. 34
2.6.9.3. by Other Halides. 36
2.6.10. Cleavage of Group-IlIB-Carbon Bonds. 38
2.6.10.1 by Halogens. 38
2.6.10.2. by Hydrogen Halides. 39
2.6.10.3. by Other Halides. 40
2.6.11. from Cleavage of the Group-IIIB-Other
Group-IVB Element Bond. 42
2.6.1 1.1, by Halogens. 42
2.6.1 1.2. by Hydrogen Halides. 44
2.6.1 1.3. by Other Halides. 46
2.6.12. from Halide-Halide Exchange Reactions
(Met at hes is ) 47
2.6.12.1. by Hydrogen Halides. 47
2.6.12.2. by Metal and Nonmetal Halides. 48
2.6.12.3. by Fluorinating Agents. 50
2.6.13. Cleavage of Other G roup -l I IB -Element
Bonds. 52
2.6.13.1. by Halogens. 52
2.6.13.2. by Hydrogen Halides. 54
2.6.13.3. by Other Halides. 54
2.6.14. Subvalent Group-IIIB Halides. 56
2.6.14.1. Boron, Aluminium, Gallium, Indium. 56
2.6.14.2. Thallium. 59
2.6.15. from Scrambling Reactions. 60
2.6.16. Miscellaneous Modes of Formation. 64
2.7. The Formation of the Halogen-Group-IA
(Li, Na, K, Rb, Cs, Fr) and Group-IIA
(Be, Mg, Ca, Sr, Ba, Ra) Metal Bond 69
2.7.1. Introduction. 69
2.7.2. from the Elements. 71
2.7.3. by Halogenation 74
Contents of Volume 4 vii
2.7.3.1. with Hydrogen Halides. 74
2.7.3.2. with Miscellaneous Halides. 75
2.7.3.2.1. from Group-IA and Group-IIA Metals
with Halides (Metal and Nonmetal). 75
2.7.3.2.2. from Alkaline-Earth Metals with
Carbon-Halogen Compounds
(Formation of Organomagnesium
Reagents). 76
2.7.4. from Reaction of Halogens with
Hydroxides, Carbonates, etc., of Group-
IA and Group-IIA Metals (Formation of
Halides by Disproportionation of the
Halogen). 78
2.7.5. from Reaction of Hydrogen Halides with
Oxides, Hydroxides, Carbonates, etc., of
the Group-IA and Group IIA Metals. 81
2.7.6. from Reaction of Oxides with Halogens. 87
2.7.7. from Reactions of Oxides of the Group-
IIA Metals with Nonmetal Halides
(Excl ud in g Hydrogen Ha I ides) . 88
2.7.8. from Reaction of Carbides of the
Elements with Halogen and Hydrogen
Halides. 91
2.7.9. from Metathetical Reactions (Anion-
Halide Exchange). 92
2.8. The Formation of the Halogen-Group16
(Cu, Ag, Au) or Group46 (Zn, Cd, Hg)
Metal Bond 96
2.8.1. Introduction. 96
2.8.2. from the Elements. 96
2.8.3. Synthesis of the Group-IB Trihalides. 99
2.8.3.7. from the Metals. 99
2.8.3.1.1. by Halogenation. 99
2.8.3.1.2. by Nonmetal Halides. 100
2.8.3.1.3. from Lower Valent Compounds. 100
2.8.3.1.4. from Metal Oxides. 101
2.8.3.1 -5. by Halogen Exchange. 101
2.8.4. Synthesis of Complex Halide Derivatives. 101
2.8.4.1. Tetrahalo Derivatives. 101
2.8.4.2. Cyanohalo Derivatives. 105
2.8.5. Synthesis of Organo Group-IB Halides. 106
2.8.6. Synthesis of Complexes of Au Trihalides
by the Halogenation of Au(l) Complexes. 109
viii Contents of Volume 4
2.8.6.1. Complexes with Group-VB Donors. 109
2.8.6.2. Complexes with Group-VIB Donors. 111
2.8.7. Synthesis of the Group-IB Dihalides from
the Metals. 113
2.8.7.1. by Halogenation Reactions. 113
2.8.7.2. by Hydrohalogenation Reactions. 114
2.8.7.3. by Hydrohalic Acids. 114
2.8.8. Synthesis of Group-IB Dihalides by Other
Procedures. 116
2.8.8.1. by Halogenation of Lower Valent
Halides. 116
2.8.8.2. by Halogenation of Metal Oxides. 117
2.8.8.3. by Reactions of Metal Oxides with
Hydro ha1i c Acids. 118
2.8.9. from Dehydration of Hydrates of the
Group-IB Dihalides. 118
2.8.10. Synthesis of Complex Halides Derived
from the Dihalides of Group-IB. 120
2.8.11. Synthesis of Group-IB Monohalides. 124
2.8.1 1. I. by Halogenation of the Metals. 124
2.8.1 1.2. by Reduction of Higher Valent Halides. 126
2.8.12. Synthesis of Complex Halides Derived
from Monohalides of Group-IB. 127
2.8.13. Synthesis of Ag Subfluoride. 133
2.8.14. Synthesis of the Group-IIB Dihalides from
the Metals. 134
2.8.14.1. by Halogenation Reactions. 134
2.8.14.2. by Hydrohalogenation Reactions. 135
2.8.14.3. by Hydrohalic Acids. 136
2.8.14.4. by Nonmetal Halides. 136
2.8.14.5. by Metal Halides. 138
2.8.15. Synthesis of the Group-IIB Dihalides from
Metal Oxides. 138
2.8.1 5.1. by Halogenation. 138
2.8.15.2. by Hydrogen Halides and Hydrohalic
Acids. 138
2.8.15.3. by Other Halogenating Agents. 139
2.8.16. Synthesis of the Group-IIB Dihalides from
Metal Sulfides. 141
2.8.16.1. by Halogenation. 141
2.8.16.2. by Other Halogenating Agents. 141
2.8.17. Synthesis of Group-IIB Halides from
Metal Oxy Salts. 142
2.8.17.1. by Hydrogen Halides and Hydrohalic
Acids. 142
Contents of Volume
4 ix
2.8.17.2. by Metathesis Reactions. 143
2.8.17.3. by Other Halogenating Agents. 143
2.8.18. Synthesis of the Group-IIB Dihalides by
Hal ide-Hal ide Exchange. 144
2.8.19. Synthesis from Dehydration of Hydrates
of the Group-IIB Dihalides. 145
2.8.20. Synthesis of Mercury(l1) Halides from
Mercury(1) Halides. 147
2.8.20.1. by Halogenation. 147
2.8.20.2. by Disproportionation Reactions. 148
2.8.21. Synthesis of Mercury(1) Halides. 148
2.8.21.1. by Metathesis Reactions of Other
Mercury(1) Salts. 148
2.8.21.2. by Reduction of Mercury(l1) Halides. 149
2.8.21 -3. by Oxidation of the Mercury Metal. 151
2.8.22. Synthesis of Complex Halides of Group-
IIB. 152
2.8.23. Synthesis of Organo Group-IIB Halides. 158
2.8.23.1. by Oxidative Addition of Alkyl and Aryl
Halides to the Metals. 158
2.8.23.2. by Transmetallation Reactions Involving
the Metal Halides. 159
2.8.23.3. by Halogenation of Alkyl Mercury
Derivatives. 162
2.8.23.4. by Reactions of Dialkyls with Acid
Chlorides. 163
2.8.23.5. by Reactions of the Dialkyls and Metal
and Nonmetal Halides. 165
2.8.23.6. by Cleavage of the C-H Bond by
Mercuric Halides. 165
2.9. Formation of the Halogen-Transition
and -Inner-Transition-Metal Bond. 167
2.9.1. Introduction. 167
2.9.2. by Direct Reaction of the Metals with
Halogens. 167
2.9.2.1. Synthesis of Metal Fluorides from the
Ele me nt s. 167
2.9.2.2. of Metal Chlorides from the Elements. 170
2.9.2.3. of Metal Bromides from the Elements. 173
2.9.2.4. of Metal Iodides from the Elements. 175
2.9.3. Synthesis of Metal Halides from the
Metals. 177
2.9.3.1. by Halogenation. 177
X Contents of Volume 4
2.9.3.2. from the Metal and Anhydrous
Hydrogen Halides. 177
2.9.3.3. by Hydrohalic Acids. 179
2.9.3.4. by Fluorination with Interhalogens. 180
2.9.3.5. of Transition-Metal Halides by
Chlorination of the Metal by Sulfuryl
Chloride. 181
2.9.3.6. of Transition-Metal Halides by
Halogen at io n with No n-Tr ans it io n-
Metal Halides. 181
2.9.3.7. of Transitional-Metal Halides
Electrochemically. 182
2.9.3.8. of Transition-Metal by Oxidative
Addition by Alkyl Halides. 185
2.9.4. Synthesis of Metal Halides from Metal
Oxides. 186
2.9.4.1. by Halogenation. 186
2.9.4.2. and Hydrogen Halide. 187
2.9.4.3. and Hydrohalic Acid. 188
2.9.4.4. by Fluorination by Interhalogens. 189
2.9.4.5. by Chlorination by Thionyl Chloride. 189
2.9.4.6. by Chlorination with CCI, and Other
Chlorocarbons. 191
2.9.4.7. by Phosgene Chlorination. 193
2.9.4.8. by Halogenation by Aluminium
Halides. 193
2.9.5. Synthesis of Metal Halides from Metal
Sulfides. 194
2.9.6. Synthesis of Metal Halides from Metal
Carbonyls. 195
2.9.7. Synthesis of Metal Halides from Metal
Carboxylates by Reaction with Acetyl
Halide or Hydrohalogenation Reactions. 196
2.9.8. Synthesis of Metal Halides from Other
Metal Salts. 198
2.9.9. Dehydration of Metal Halide Hydrates. 198
2.9.9.1. by Dehydration of Hydrohalogenation
Reactions. 198
2.9.9.2. by Chemical Methods. 199
2.9.10. Synthesis of Complex Halo Anions 200
2.9.10.1. by Reaction of Metal Halides with Non-
Transition-Metal and Organic Halides. 200
2.9.10.2. by Reaction of Metal Oxides with
Hydrohalic Acids. 208