Inorganic Chemistry of the Main-Group Elements Volume 2

742 Pages·1974·38.658 MB·English

by  C C Addison

A Specialist Periodical Report
Inorganic Chemistry of the Main-group
Elements
Volume 2
A Review of the Literature Published between
September 1972 and September 1973
Senior Reporter
C. C. Addison
Reporters
M. G. Barker
G. Davidson
M. F. A. Dove
P. G. Harrison
P. Hubberstey
A. Morris
R. J. Pulham
D. B. Sowerby
All of: Deportment of Chemistry, Univeisity of Nottinghani
@ Copyright 1974
The Chemical Society
Burlington House, London WIV OBN
ISBN :0 85186 762 6
Library of Congress Catalog Card No 72-95098
Printed in Northern Ireland at The Universities Press, Belfast.
Preface
The framework used in Volume 1 for reporting the Chemistry of the Main-
group Elements appears to have been generally acceptable, and has been
continued in Volume 2. The present volume therefore comprises eight
chapters, each concerned with one of the Main Groups as defined in the
abbreviated form of the Periodic Table given in the Preface to Volume 1, and
it has now been agreed that the chemistry of zinc, cadmium, and mercury will
be included in the Specialist Periodical Reports concerned with the Transition
.
Elements
The relative sizes of the chapters are much the same as in Volume 1 and this
again reflects the amount of published research in each Group. In Chapter 1,
greater coverage is given to those properties of the metals which are relevant
to their use in the generation of electrical energy from batteries, or from
nuclear fission and fusion reactors, and both Chapters 1 and 2 include more
illustrative material. Chapter 3 reflects a steady increase in effort throughout
the Group, but an especially large number of papers have been published on
carbaborane r-complexes. Chapter 4 is large, consistent with the considerable
amount of research which continues to be published on each of these elements.
Chapter 5 now includes a short section on ‘nitrogen oxides and atmospheric
chemistry,’ but the bulk of published material is again concerned with the
chemistry of phosphorus; there are some 500 references to phosphorus,
whereas arsenic, antimony, and bismuth together are covered by 240
references. Careful selection has been necessary in Chapter 6 to avoid overlap
with other chapters or volumes. Thus, this chapter contains the chemistry of
sulphides of Main-group elements, but not sulphides of transition metals.
Again, S-N compounds are dealt with in this chapter, whereas S-B com-
pounds are in Chapter 3, and S-P and S-As compounds in Chapter 5. The
halides of the elements are treated as they arise in Chapters 1-6, and Chapter
7 is restricted to interesting recent developments in halogen chemistry, such
as the superacids. Noble-gas chemistry is represented by a small number of
highly interesting papers, which are discussed in Chapter 8.
We have continued the policy of referring to physical properties (and
particularly spectroscopic data) of compounds only where this is essential to
demonstrate some important chemical property, Similarly, we refer only to
those aspects of organo-derivatives which illustrate significant features in the
chemistry of the Main-group element involved. On the other hand, more
structures are becoming available (often highly refined) now that X-ray
diffraction methods are becoming computerized; the chemistry becomes more
meaningful, and is more readily explained, once the structure is known, and
other physical measurements become less significant. We have therefore taken
every opportunity to include structures of key compounds.
The whole volume is again written by members of the Department of
Chemistry in the University of Nottingham, so that the maximum degree of
...
111
iv Preface
consultation has been possible. In spite of this, and in spite of the fact that the
period of coverage of Volume 2 is from September 1972 to September 1973
(i.e. 12 months as against 15 months for Volume l), Volume 2 is appreciably
longer. This is not due entirely to the enthusiasm of the authors; with ex-
perience, it has become easier to identify developing themes, and to discuss
them meaningfully, and we have the impression that the amount of research
effort devoted to the Main-group elements is increasing.
C. C. Addison
Contents
Chapter 1 Elements of Group I 1
By R. I. Pulhom
Introduction 1
The Alkali Metals 1
Alloys and Intermetallic Compounds 11
Solvation of Alkali-metal Ions 13
Aqueous Solvation 13
Non-aqueous Solvation 17
5 Compounds containing Organic Molecules or Complex
Ions 25
6 Alkali-metal Oxides 34
7 Alkali-metal Halides 38
8 Lithium Compounds 42
9 Sodium Compounds 49
10 Potassium Compounds 53
11 Rubidium Compounds 56
12 Caesium Compounds 57
13 Analysis 58
14 Molten Salts 60
Nitrates 61
Halides 64
Chapter 2 Elements of Group II 73
By R. J. Pulham
Beryllium 73
Magnesium 77
Calcium 86
Strontium 92
Barium 95
6 Analysis 99
V
vi Cont ents
Chapter 3 Elements of Group Ill 103
By G. Davidson
1 Boron 103
General 103
Boron Hydrides 1 04
Borane Anions and their Derivatives 110
Carbaboranes and their Metallo-derivatives 117
Aminoboranes and other Compounds containing B- -N
Bonds 139
Compounds containing B-P or B-As Bonds 144
Boron Halides 147
Compounds containing B-0 Bonds 151
Compounds containing B-C Bonds 158
Boron-containing Heterocycles 160
Compounds containing B-S Bonds 170
Boron Nitride and Metal Borides 171
2 Aluminium 174
General and Analytical 174
Aluminium Hydrides 174
Compounds containing AI-C and Al-Si Bonds 177
Compounds containing Al-N Bonds 179
Compounds containing A1-0 or AI-S Bonds 183
Aluminium Halides 193
Other Aluminium Compounds 198
3 Gallium 199
General and Analytical 199
Compounds containing Ga-N Bonds 199
Compounds containing Ga-0 or Ga-S Bonds 201
Gallium Halides 204
Other Gallium Compounds 206
4 Indium 207
General and Analytical 207
Compounds containing In-0, In-S, or In-Se Bonds 208
Indium Halides 212
Other Indium Compounds 215
5 Thallium 216
General and Analytical 216
Thallium(1n) Compounds 217
Thalliurn(1) Compounds 219
Other Thallium Compounds 224
Contents vi i
Chapter 4 Elements of Group IV 225
By P. G. Harrison and P. Hubberstey
1 Carbon 225
Allotropes 225
Vapour-phase Species 226
Diamond 227
Graphite 228
Vitreous Carbon 230
Carbyne 230
Carbon Fibres 230
Surface, Adsorption, and Catalytic Studies 23 1
Oxidation Studies 232
Carbides 235
Graphite Intercalation Compounds 238
Alkali Metals. 239
Halogens, Halides, Oxides, and Acids 240
Methane and its Substituted Derivatives 242
Methane 242
Halogenometh anes 245
Other Substituted Methanes 254
Formaldehyde and its Substituted Derivatives 260
Formaldehyde, Thioformaldehyde, Carbonyl Hal-
ides, and Thiocarbonyl Halides 260
Formic Acid and Formates 263
Derivatives of Group VI Elements 265
Oxides, Sulphides, and Related Species 265
Carbonates, Thiocarbonates, and Related Anions 276
Derivatives of Group V Elements 28 1
Cyanogen and Cyanides 28 1
Cyanates and Related Species 287
2 Silicon, Germanium, Tin, and Lead 290
Hydrides of Silicon, Germanium, Tin, and Lead 290
Halides of Silicon, Germanium, Tin, and Lead 297
Synthesis 297
Reactions of Silicon, Germanium, and Tin Tetra-
halides and Related Compounds 301
Physical Studies of Quadrivalent Silicon, Germa-
nium, and Tin Halides 304
(i) Structural studies 304
(ii) Infrared, Raman, and microwave data 305
(iii) N.m.r. studies 306
(iv) Mossbauer studies 306
viii Contents
(v) Miscellaneous studies 307
Complexes and Complex Anions 307
(i) Halide donors 307
(ii) Oxygen donors 308
(iii) Sulphur donors 3 14
(iv) Nitrogen donors 3 14
(v) Phosphorus donors 315
Oxygen Derivatives of Silicon, Germanium, Tin, and
Lead 315
Silicon Solid-state Chemistry 316
(i) Silicon Dioxide 316
(ii) Silicates 324
(iii) Aluminosilicates 336
(iv) Zeolites 341
Germanium(1v) Oxide and Germanates 350
Tin(rv) Oxide and Stannates 352
Lead(xv) Oxide and Plumbates 353
Molecular Oxides 354
Alkoxides 358
Carboxylates 362
Oxyacid Derivatives 364
Miscellaneous Derivatives 367
Silicon, Germanium, Tin, and Lead Derivatives of
Sulphur, Selenium, and Tellurium 369
Thio-germanates, -stannates, and -plumbates, and
Related Systems 369
Molecular Compounds containing M-S, -Se, and
-Te (M = Si, Ge, Sn, or Pb) Bonds 370
Compounds containing Silicon-, Germanium-, Tin-,
and Lead-Nitrogen Bonds 372
Phosphorus and Arsenic Derivatives of Silicon,
Germanium, and Tin. 382
Pseudohalide Derivatives of Silicon, Germanium, and
Tin. 382
Derivatives containing Silicon-, Germanium-, and
Tin-Main-group Metal Bonds 383
Bonds to Group IV Metals 383
Bonds to Group 111 Metals 386
Transition-metal Derivatives of Silicon, Germanium,
Tin, and Lead 388
Bivalent Derivatives of Silicon, Germanium, Tin, and
Lead 402
Sily lenes 402
Germanium(n), Tin@), and Lead(@ Halides and
Halide Complexes 405