Embed Size (px)
Citation preview
Inorganic Reactions and Methods
Volume 17 Oligomerization and Polymerization Formation of Intercalation Compounds
Founding Editor
J.J. Zuckerman
Editor
A.P. Hagen
8 WILEY-VCH
Inorganic Reactions and Methods
Volume 17
Inorganic Reactions and Methods
Editor
Professor A.P. Hagen Department of Chemistry The University of Oklahoma Norman, Oklahoma 73019
Editorial Advisory Board
Professor N. Bartlett Department of Chemistry University of California at Berkeley Berkeley, California 94720
Professor F.A. Cotton Department of Chemistry Texas A&M University College Station, Texas 77840
Professor E.O. Fischer Anorganisch-chemisches Laboratorium
D-8046 Garching Lichtenbergestrasse 4 Federal Republic of Germany
Professor P. Hagenmuller Laboratoire de Chemie du Solide du
351 cours de la Liberation F-33405 Talence France
Professor M.F. Lappert The Chemical Laboratory University of Sussex Falmer, Brighton, BN1 9A3 England
der Technischen UniversitM
C.N.R.S.
Professor A.G. MacDiarmid Department of Chemistry University of Pennsylvania Philadelphia, Pennsylvania 191 74
Professor M. Schmidt lnstitut fur Anorganische Chemie der
Universitat D-8700 Wurzburg Am Hubland Federal Republic of Germany
Professor H. Taube Department of Chemistry Stanford University Stanford, California 94305
Professor L.M. Venanzi Laboratorium fur Anorganische Chemie
der ETH CH-80006 Zurich Universitatsstrasse 5 Switzerland
Professor Sir Geoffrey Wilkinson, F.R.S. Department of Chemistry Imperial College South Kensington London, SW7 2AY England
@ 1990 VCH Publishers, Inc , New York
Distribution: VCH Verlagsgesellschafi mbH, P.O. Box 1260/1280, D-6940 Weinheim, Federal Republic of Germany USA and Canada: VCH Publishers, Inc., 303 N.W. 12th Avenue, Deerfield Beach, FL 33442-1705, USA
Inorganic Reactions and Methods
Volume 17 Oligomerization and Polymerization Formation of Intercalation Compounds
Founding Editor
J.J. Zuckerman
Editor
A.P. Hagen
8 WILEY-VCH
@ 1990 VCH Publishers, Inc.
This work is subject to copyright.
All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photo- copying machine or similar means, and storage in data banks.
Authorization to photocopy items for internal or personal use, or the internal or personal use of specific clients, is granted by VCH Publishers, Inc. for libaries and other users registered with the Copyright Clearance Center (CCC) Transactional Reporting Service, provided that the base fee of $1.00 per copy, plus $0.25 per page is paid directly to CCC, 27 Congress Street, Salem, MA 01 970.
Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
ISBN 0-471-18667-8
ISBN 3-527-26275-X VCH Verlagsgesellschaft
Contents of Volume 17
How to Use this Book Preface to the Series Editorial Consultants to the Series Contributors to Volume 17
15.
15.1.
15.1 .l. 15.1.1.1. 15.1.1.2. 15.1.1.3. 15.1.1.3.1.
15.1.1.3.2. 15.1.1.3.3.
15.1.1.3.4.
15.1.2.
15.1.2.1.
15.1.2.2.
15.1.3.
15.1.3.1. 15.1.3.2.
15.1.3.2.1. 15.1.3.2.2.
Oligomerization and Polymerization
Introduction
Definitions and Scope. Definitions of Oligomers and Polymers. General Synthesis Methods. Scope.
Small-Ring Systems-Examples of Synthesis. Cag es-Exam p I es of Synthesis. Short C hai ns-Exam ples of Synthesis. Long Chains-Examples of Synthesis.
Characteristic Differences Between Small and Large Molecules as Related to Their Synthesis.
Special Characteristics of Small Cyclic and Linear Molecules. Special Characteristics of Long-Chain Molecu I es.
C hai n-C h ai n , C h a i n-R i ng and R i ng-R i ng Equilibria.
Bond Lability in Inorganic Systems. Some Important Relationships Based on Theory.
The Chain Population. The Ring Population and Network Macromolecules.
1
7 12
13
15
17
17
18
19 20
21 22
24
V
vi Contents of Volume 17 ~~
15.1 Introduction
15.1.3.3. Scrambling in Inorganic Systems. 15.1.3.3.1. All-Neso Systems. 15.1.3.3.2.
15.1.3.3.3. Exchange of Segments Between
15.1.3.3.4.
Oligomers and Polymers in QZ,-QT, Systems with Z Bridging.
C yc I ic M o I ecu les. Chains and Rings from Scrambling Between Two Kinds of Central Moieties.
15.2.
15.2.1. 15.2.2.
15.2.2.1. 15.2.2.2. 15.2.2.2.1. 15.2.2.2.2.
15.2.2.2.3. 15.2.2.2.4.
15.2.2.2.5.
15.2.2.2.6.
15.2.2.2.7. 15.2.2.2.8. 15.2.2.2.9.
15.2.2.2.10.
15.2.2.2.11.
15.2.2.2.12. 15.2.2.2.13.
15.2.2.2.14.
Ring-Ring and Ring-Polymer Interconversions
Introduction. lnterconversion of Sulfur or Selenium Rings and Chains
Theory . Ex pe r i mental Techniques
Viscosity Measurements. Ultrasonic Absorption in Liquid Selenium. Quenching Experiments. Diamagnetic Suscepti bi I ity Measurements. Paramagnetic Suscepti bi I i ty Measurements. Electron Spin Resonance Absorption (ESR). Optical Absorption. Vibrational Spectroscopy of Sulfur. Nuclear Magnetic Resonance (NMR) Measurements on Selenium. Dielectric Constant Measurements of Su Ifu r. Specific Heat Measurements on Sulfur and Selenium. Density Measurements. Thermal Conductivity in Liquid Selenium. Electrical Conductivity of Sulfur.
26 26
31
33
34
37
37
39 39 46 46
47 47
48
48
50 50 51
51
51
52 52
53 53
Contents of Volume 17 vi i
15.2.3.
15.2.3.1. 15.2.3.2. 15.2.3.3. 15.2.3.4. 15.2.3.5. 15.2.4. 15.2.4.1.
15.2.4.1 .l. 15.2.4.1.2. 15.2.4.1.3. 15.2.4.1.4. 15.2.4.2. 15.2.4.2.1. 15.2.4.2.2. 15.2.4.2.3. 15.2.4.3.
15.2.4.4. 15.2.4.5. 15.2.5. 15.2.5.1. 15.2.5.1 .l. 15.2.5.1.2. 15.2.5.2.
15.2.5.3.
15.2.5.4.
15.2.5.5.
15.2.5.5.1. 15.2.5.5.2. 15.2.6
15.2.6.1. 15.2.6.2. 15.2.6.3. 15.2.6.4.
15.2.7.
In Oligomeric Catenates of P, As, Sb and Bi.
General Trends. Phosphorus. Arsenic. Antimony. Stabilized Rings and Chains.
Formation of Cyclic Silicon-Silicon Systems.
In Silicon-Silicon Systems.
Perarylcyclosilanes. Permethylcyclosilanes. Other Peralkylcyclosilanes. A I ky I a r y lcycl osi I anes .
Reactions of Cyclosilanes. Substitutional Reactions. Ring-Cleavage Reactions. Photo1 ysis.
Ring-Ring and Chain-Ring Interconversion. Cage Polysilanes. Silane High Polymers.
in Boron-Nitrogen Systems. Synthesis of Ring Compounds
Borazines and Related Compounds. Coordinately Saturated B-N Rings.
Factors Affecting Stability of Ring Species. Preparation of Linear Boron-Nitrogen 01 i gomers. lnterconversions in Boron-Nitrogen Systems. Preparation of Boro n-N it r og e n Polymers.
Linear Boron-Nitrogen Chains. Polycyclic Chains.
in Boron-Oxygen and Boron-Sulfur Systems
An ion ic Boron-Oxyg e n Compounds. Molecular Boron-Oxygen Species. Boron-Su Ifu r Com pou nds. Ring-ring and Ring-chain interconversions.
in Cage Polyboranes and Carboranes.
53 53 54 55 58 59 61
61 61 62 66 66 69 69 71 74
75 79 80 83 83 83 86
87
88
89
90 90 91
93 93 94 95
96 97
viii Contents of Volume 17
15.2
15.2.7.1.
15.2.7.2.
15.2.7.3.
15.2.8. 15.2.8.1. 15.2.8.2. 15.2.8.3.
15.2.8.4.
15.2.8.5. 15.2.9.
15.2.9.1. 15.2.9.2.
15.2.9.3.
15.2.9.4. 15.2.9.5.
15.2.9.6.
15.2.1 0. 15.2.10.1.
15.2.10.2. 15.2.10.3. 15.2.10.4. 15.2.1 1.
15.2.1 1 . I . 15.2.11.2.
15.2.1 1.3.
15.2.1 1.4.
Ring-Ring and Ring-Polymer Interconversions
Polyborane Oligomers and Polymers; Syntheses. Preparation of Carborane-Siloxane Polymers. Preparation of Other Carborane- Incorporated Inorganic Polymers.
Formation of Cyclic Oligomers. Cyclosiloxane Structural Diversity. Ring-Ring Equilibration of Cyc Ios i loxanes. R i ng-C hai n Eq u i I i b rat i o n : Polymerization of Cyclosiloxanes. End-Capping Reactions.
in Silicon-Nitrogen and Silicon-Sulfur Systems.
Si I icon-Oxygen Systems
Silicon-Nitrogen Syntheses. Si I icon-N i t rogen Ri ng-Ri ng I nterconversions. Cyclic Silicon-Nitrogen Oligomers Polymerization. Si I icon-Su If u r Syntheses. Si I icon-Su If u r Ri ng-Ri ng Interconversions. Cyclic Si I icon-Sulfu r 01 igomer Polymerization.
i n Phosphor us-Oxyg e n Systems Reorganized Mixtures of Chains and Rings. Preparation of Cyclic Polymers. Chain Oligomers and Macromolecules. Related Mixed Systems.
Halocyclophosphazene Polymerization Organocyclophosphazenes: Ring-Ring and Ring-Polymer Interconversions Mechanisms and Thermodynamics of Phosphazene Equilibrations. Polyorganophosphazenes via the Reactions of Polydihalophosphazenes.
in Phosphorus-Nitrogen Oligomers and Polymers
98
99
103 105 107 108
112
114 115
116 116
118
137 139
142
142 143
144 145 148 150
151 151
154
159
161
Contents of Volume 17 ix ~
15.2.12. 15.2.12.1. 15.2.12.2.
15.2.12.3. 15.2.12.4. 15.2.12.5.
15.2.12.6.
15.2.12.7. 15.2.12.8.
15.2.12.9.
15.2.1 2.10.
15.2.13.
15.2.13.1. 15.2.13.2. 15.2.13.2.1. 15.2.13.2.2.
15.2.13.2.3. 15.2.13.3. 15.2.13.3.1. 15.2.13.3.2. 15.2.13.3.3. 15.2.13.3.4. 15.2.13.3.5.
15.2.13.3.6.
15.2.13.4. 15.2.13.5.
15.2.13.6.
15.2.14. 15.2.14.1. 15.2.14.2.
in Su Ifur-Ni trogen 01 igomers and Polymers Formation of the Monomer SN Formation of Cyclic Oligomers (SN), and (SN),. Polymerization of (SN), to (SN),. Halogenated Derivatives of (SN),. Formation of Cyclic Oligomers (NSX). (X = CI, F; n = 3,4). Formation of the Cyclic Oligomers
Formation of the Cyclic Oligomer (SNH),. Formation of Thionyl lmide Polymers (HNSO),. S-N Oligomers with Terminal Organic Groups. S-Polymers with Organic Groups in the Backbone.
Polymers Containing Metal-Oxygen and Metal-Carbon Bonds
“S(O)XI,.
Introduction. M-C-Containing Polymers
Metallocenes. Polycarbosilanes, Polysilarylenes, Polycarbosiloxanes and Po I y (ca r bo rane-s i I oxanes) . Other Metallorganic Compounds.
M-0-Contai n i ng Polymers In organic Po I ys i I icas. Po I y m eta1 Ios i I oxan es. Pol y(si I yl arylene si loxanes). Polyarylsilsesquioxanes. Polymetal Phosphinates and Polyphosphonatolanes Miscellaneous.
0 II
M-0-C-Containing Polymers. M-0-R (Pol yet her)-Con tai n i ng Polymers. M-0-N-Contain i ng Polymers (Polyamidoximes and Polyoximes).
Introduction. General Synthetic Routes.
Coordination Polymers
172 172
173 174 175
176
177 178
178
179
180
180 180 181 181
184 185 187 187 187 188 190
190 191
191
192
193 194 194 194
X Contents of Volume 17
15.2
15.2.14.3. 15.2.14.4. 15.2.14.5. 15.2.14.5.1. 15.2.14.5.2.
15.2.14.5.3. 15.2.14.5.4. 15.2.14.5.5.
16.
16.1.
16.2.
16.2.1. 16.2.2.
16.2.2.1. 16.2.2.2. 16.2.2.3. 16.2.3.
16.2.3.1.
16.2.3.2.
16.3.
16.3.1. 16.3.1.1.
16.3.1.2. 16.3.1.3.
Ring-Ring and Ring-Polymer lnterconversions
lonomers. Pro per ty-St r uct u re P r i nci p I es . Selected Polymers.
Metal Phosphinates. Platinum and Pd Coordination Polymers. Uranyl Ion Complexation. Bis-P-diketone-Based Polymers. Bisthiopiocol inam ide-Based Polymers.
Formation of Intercalation Compounds
Introduction
The Formation of Clathrates
Definitions The Formation of Clathrates Having a Water Host Lattice
Clathrates of the Gas Hydrate Type. Clathrates of the Liquid Hydrate Type Other Clathrate Hydrates.
The Formation of Clathrates Having a Silicon, Germanium and Tin Host Lattice
The Formation of Silicon and Germanium Clathrates by Thermal Decomposition of Silicides and Germanides. The Formation of Silicon, Germanium and Tin Clathrates from the Elements.
The Formation of Tunnel Structures
Ion Exchange Zeolites with Intersecting Tunnel Frameworks. Pyrochlores A, xxM20, A2M,0,, Structure and lntergrowths with Pyrochlores.
200 200 201 20 1
202 203 204
205
207
208
209
209
210 21 1 214 215
219
22 1
222
223 223
223 226
228
Contents of Volume 17 xi
16.3.1.4.
16.3.1.5.
6.3.1 -6. 6.3.2. 6.3.2.1. 6.3.2.2.
6.3.2.2.1. 16.3.2.2.2. 16.3.2.3. 16.3.2.3.1. 16.3.2.3.2.
16.3.2.3.3.
16.4.
16.4.1. 16.4.2.
16.4.2.1. 16.4.2.1.1. 16.4.2.1.2. 16.4.2.1.3. 16.4.2.1.4. 16.4.2.1 -5. 16.4.2.2. 16.4.2.2.1.
16.4.2.2.2.
16.4.2.3.
16.4.2.4.
16.4.2.4.1
16.4.2.4.2.
Alkali Antimonates K,Sb,O,, and
Ammonium and Potassium 12 Molybdophosphates A3P04Mo,2036. Structures with Parallel Tunnels
Rate of Growth of Deposit. Mechanism of Electrochemical Preparation of Tungsten Bronzes
Nature of the Reduced Species. Reactions at the Electrodes.
Experimental Procedure and Data the Electrolyte Cell. Effect of the Melt Composition and Temperature. Examples of Oxides with Tunnel Structures Obtained by Molten Salt Electrolysis.
KC$ b501 4'
by Electrolysis
The Formation of Sheet Structures
In trod ucti on. Graphite and Boron Nitride Intercalation Compounds
Hal ides. Oxyhalides. Oxides. Acids. Halogens and Interhalogens.
Synthesis of Graphite and Carbon Intercalation Compounds Containing One metal. Graphite Intercalation Compounds Containing Two Metals (Ternary Com pou nds).
Electron Acceptors
Electron Donors
Mixed Metal-Molecule-Graphite Ternaries. Al ka I i-M etal-Hydrogen42 rap h i te Ternaries.
Hydrogenation of the binary phases MC, and MC,, (M = K, Rb, Cs). Intercalation of Alkali-Metal Hydrides into Graphite.
228
228 229 229 230
230 230 23 1 232 232
232
234
237
237
238 238 238 243 244 245 246 247
247
25 1
255
257
257
257
xii Contents of Volume 17
16.4
16.4.2.4.3.
16.4.2.4.4.
16.4.2.5. 16.4.2.5.1.
16.4.2.5.2. 16.4.2.5.3. 16.4.2.5.4. 16.4.2.6. 16.4.2.6.1.
16.4.2.6.2. 16.4.2.6.3.
16.4.2.7. 16.4.2.7.1. 16.4.2.7.2. 16.4.2.7.3. 16.4.2.8. 16.4.2.8.1.
16.4.2.8.2. 16.4.2.8.3. 16.4.3. 16.4.3.1. 16.4.3.2. 16.4.3.3. 16.4.3.4. 16.4.3.5.
16.4.3.6.
16.4.4. 16.4.5. 16.4.6. 16.4.7. 16.4.7.1. 16.4.7.2.
The Formation of Sheet Structures
Intercalation of Quaternary Compounds with Hydrogen and Two Alkali Metals into Graphite. Physiosorption of Hydrogen and Deuterium in the Second-Stage Compounds MC,,(M = K, Rb or Cs)
Definition and Nomenclature of Graphite Oxides. Preparation of Graphite Oxides. Reactivity of Graphite Oxides. Graphite Oxide Membranes.
Poly(monocarbon monofluoride),
Pol y (d icar bon monof I uo r i de) , (C,F) . Poly(tetracarbon monofluoride),
Residue and Surface Compounds Introduction and Definitions. Preparation of Residue Compounds. Preparation of Surface Compounds. Electrochemical Formation. Strengths and Limitations of the
Cathodic Reduction of Graphite. Anodic Oxidation of Graphite.
Graphite Oxides
Graphite Fluorides
(CF) n -
(C4F)n.
Electrochemical Technique.
Dichalcogenides Layered Dichalcogenides. Alkali-Metal intercalates. Electrochemical Formation Molecular Intercalates. Hydrated and Solvated Alkali-Metal Phases. Intercalation-Substitution Compounds and Ionic Mobility
Trichalcogenohypophosphates. Transition-Metal Oxyhalides. Lamellar Oxides. Lamellar Silicates and Related Materials.
Lamellar Silicates. lntercalation Products.
259
259 259
260 26 1 263 265 265
265 269
270 27 1 27 1 272 274 276
276 280 281 284 284 288 295 300
306
308 309 31 3 31 8 323 324 328
Contents of Volume 17 xiii ~
16.4.8.
16.4.8.1.
16.4.8.2.
16.4.8.3. 16.4.8.4. 16.4.8.5.
16.4.8.6. 16.4.8.7.
The Chemical Reactivity of Low- Dimensional Solids
The Electronic Transfer and the Formation of Cationic Intercalation Compounds. Structural Charges Induced by Electronic Transfer. Strong Ion-Electron Coupling. Microdomains in MPS, Phases. Electronic Transfer and Ac Parameter Expansion. Acidobasic Topochemical Reactions. “Internal Surfaces” Grafting Chemistry.
List of Abbreviations Author Index Compound Index Subject Index
33 1
332
333 335 337
338 339
340
34 1 000 000 000
How to Use this Book
1. Organization of Subject Matter
1.1, Logic of Subdivision and Add-on Chapters
This volume is part of a series that describes all of inorganic reaction chemistry. The contents are subdivided systematically and so are the contents of the entire series: Using the periodic system as a correlative device, it is shown how bonds between pairs of elements can be made. Treatment begins with hydrogen making a bond to itself in H, and proceeds according to the periodic table with the bonds formed by hydrogen to the halogens, the groups headed by oxygen, nitrogen, carbon, boron, beryllium and lithium, to the tran- sition and inner-transition metals and to the members of group zero. Next it is considered how the halogens form bonds among themselves and then to the elements of the main groups VI to I, the transition and inner-transition metals and the zero-group gases. The process repeats itself with descriptions of the members of each successive periodic group making bonds to all the remaining elements not yet treated until group zero is reached. At this point all actual as well as possible combinations have been covered.
The focus is on the primary formation of bonds, not on subsequent reac- tions of the products to form other bonds. These latter reactions are covered at the places where the formation of those bonds is described. Reactions in which atoms merely change their oxidation states are not included, nor are re- actions in which the same pairs of elements come together again in the prod- uct (for example, in metatheses or redistributions). Physical and spectroscopic properties or structural details of the products are not covered by the reaction volumes which are concerned with synthetic utility based on yield, economy of ingredients, purity of product, specificity, etc. The preparation of short-lived transient species is not described.
While in principle the systematization described above could suffice to deal with all the relevant material, there are other topics that inorganic chem- ists customarily identify as being useful in organizing reaction information and that do not fit into the scheme. These topics are the subject of eight additional chapters constituting the last four books of the series. These chapters are sys- tematic only within their own confines. Their inclusion is based on the best judgment of the Editorial Advisory Board as to what would be most useful currently as well as effective in guiding the future of inorganic reaction chem- istry.
xv
xvi How to Use this Book
1.2. Use of Decimal Section Numbers
The organization of the material is readily apparent through the use of numbers and headings. Chapters are broken down into divisions, sections and subsections, which have short descriptive headings and are numbered accord- ing to the following scheme:
1. Major Heading 1.1. Chapter Heading 1.1.1. Division Heading l . l . l , l , Section Heading 1.1.1,l. 1. Subsection Heading
Further subdivision of a five-digit “slice” utilizes lower-case Roman numerals in parentheses: (i), (ii), (iii), etc. It is often found that as a consequence of the organization, cognate material is located in different chapters but in similarly numbered pieces, i.e., in parallel sections. Section numbers, rather than page numbers, are the key by which the material is accessed through the various in- dexes.
1.3. Building of Headings
1.3.1. Headings Forming Part of a Sentence
Most headings are sentence-fragment phrases which constitute sentences when combined. Usually a period signifies the end of a combined sentence. In order to reconstitute the context in which a heading is to be read, superior- rank titles are printed as running heads on each page. When the sentences are put together from their constituent parts, they describe the contents of the piece at hand. For an example, see 2.3 below.
1.3.2. Headings Forming Part of an Enumeration
For some material it is not useful to construct title sentences as described above. In these cases hierarchical lists, in which the topics are enumerated, are more appropriate. To inform the reader fully about the nature of the material being described, the headings of connected sections that are superior in hierar- chy always occur as running heads at the top of each page.
2. Access and Reference Tools
2.1. Plan of the Entire Series (Front Endpaper)
Printed on the inside of the front cover is a list, compiled from all 18 re- action volumes, of the major and chapter headings, that is, all headings that
How to Use this Book xvii
are preceded by a one- or two-digit decimal section number. This list shows in which volumes the headings occur and highlights the contents of the volume that is at hand by means of a gray tint.
2.2. Contents of the Volume at Hand
All the headings, down to the title of the smallest decimal-numbered sub- section, are listed in the detailed table of contents of each volume. For each heading the table of contents shows the decimal section number by which it is preceded and the number of the page on which it is found. Beside the decimal section numbers, successive indentations reveal the hierarchy of the sections and thereby facilitate the comprehension of the phrase (or of the enumerative sequence) to which the headings of hierarchically successive sections combine. To reconstitute the context in which the heading of a section must be read to become meaningful, relevant headings of sections superior in hierarchy are re- peated at the top of every page of the table of contents. The repetitive occur- rences of these headings is indicated by the fact that position and page numbers are omitted.
2.3. Running Heads
In order to indicate the hierarchical position of a section, the top of every page of text shows the headings of up to three connected sections that are su- perior in hierarchy. These running heads provide the context within which the title of the section under discussion becomes meaningful. As an example, the page of Volume 1 on which section 1.4.9.1.3 “in the Production of Methanol” starts, carries the running heads:
1.4. The Formation of Bonds between Hydrogen and O,S,Se,Te,Po 1.4.9. by Industrial Processes 1.4.9.1. Involving Oxygen Compounds
whereby the phrase “in the Production of Methanol” is put into its proper perspective.
2.4. List of Abbreviations
Preceding the indexes there is a list of those abbreviations that are fre- quently used in the text of the volume at hand or in companion volumes. This list varies somewhat in length from volume to volume; that is, it becomes more comprehensive as new volumes are published.
Abbreviations that are used incidentally or have no general applicability are not included in the list but are explained at the place of occurrence in the text.
xviii How to Use this Book
2.5. Author Index
The author index is compiled by computer from the lists of references. Thus it tells whose publications are cited and in that respect is comprehensive. It is not a list of authors, beyond those cited in the references, whose results are reported in the text. However, as the references cited are leading ones, consulting them, along with the use of appropriate works of the secondary lit- erature, will rapidly lead to the complete literature related to any particular subject covered.
Each entry in the author index refers the user to the appropriate section number.
2.6. Compound Index
The compound index lists individual, fully specified compositions of mat- ter that are mentioned in the text. It is an index of empirical formulas, ordered according to the following system: the elements within a given formula occur in alphabetical sequence except for C, or C and H if present, which always come first. Thus, the empirical formula
for Ti(SO,), is O,S,Ti
Be,CO, CBe,O, CsHBr, Br,CsH Al(HCO,), C,H,AlO,
BH, -NH, BH6N
The formulas themselves are ordered alphanumerically without exception; that is, the formulas listed above follow each other in the sequence BH,N, Br,CsH, CBe,O,, C,H,AlO,, O,S,Ti.
A compound index constructed by these principles tells whether a given compound is present. It cannot provide information about compound classes, for example, all aluminum derivatives or all compounds containing phos- phorus.
In order to open this route of access as well, the compound index is aug- mented by successively permuted versions of all empirical formulas. Thus the number of appearances that an empirical formula makes in the compound in- dex is equal to the number of elements it contains. As an example, C,H,AlO,, mentioned above, will appear as such and, at the appropriate positions in the alphanumeric sequence, as H3A109*C3, AlO,*C,H, and O,*C,H,Al. The as- terisk identifies a permuted formula and allows the original formula to be re- constructed by shifting to the front the elements that follow the asterisk.
Each nonpermuted formula is followed by linerarized structural formulas that indicate how the elements are combined in groups. They reveal the con- nectivity of the compounds underlying each empirical formula and serve to
How to Use this Book xix
distinguish substances which are identical in composition but differ in the ar- rangement of elements (isomers). As an example, the empirical formula C,H *,O might be followed by the linearized structural formulas (CH3CH2),0, CH, (CH2),0CH3, (CH,),CHOCH,, CH,(CH,),OH, (CH,),CHCH,OH and CH, CH2(CH,)CHOH to identify the various ethers and alcohols that have the ele- ment count C,H,,O.
Each linearized structural formula is followed in a third column by key- words describing the context in which it is discussed and by the number($ of the section(s) in which it occurs.
2.7. Subject index
The subject index provides access to the text by way of methods, tech- niques, reaction types, apparatus, effects and other phenomena. Also, it lists compound classes such as organotin compounds or rare-earth hydrides which cannot be expressed by the empirical formulas of the compound index.
For multiple entries, additional keywords indicate contexts and thereby avoid the retrieval of information that is irrelevant to the user’s need.
Again, section numbers are used to direct the reader to those positions in the book where substantial information is to be found.
2.8. Periodic Table (Back Endpaper)
Reference to periodic groups avoids cumbersome enumerations. Section headings in the series employ the nomenclature.
Unfortunately, however, there is at the present time no general agreement on group designations. In fact, the scheme that is most widely used (combin- ing a group number with the letters A and B) is accompanied by two mutual- ly contradictory interpretations. Thus, titanium may be a group IVA or group IVB element depending on the school to which one adheres or the part of the world in which one resides.
In order to clarify the situation for the purposes of the series, a suitable labeled periodic table is printed on the inside back cover of each volume. All references to periodic group designations in the series refer to this scheme.
Preface to the Series
Inorganic Reactions and Methods constitutes a closed-end series of books designed to present the state of the art of synthetic inorganic chemistry in an unprecedented manner. So far, access to knowledge in inorganic chemistry has been provided almost exclusively using the elements or classes of compounds as starting points. In the first 18 volumes of Inorganic Reactions and Methods, it is bond formation and type of reaction that form the basis of classification.
This new route of access has required new approaches. Rather than sew- ing together a collection of review articles, a framework has had to be designed that reflects the creative potential of the science and is hoped to stimulate its further development by identifying areas of research that are most likely to be fruitful.
The reaction volumes describe methods by which bonds between the ele- ments can be formed. The work opens with hydrogen making a bond to itself in H, and proceeds through the formation of bonds between hydrogen and the halogens, the groups headed by oxygen, nitrogen, carbon, boron, beryllium and lithium to the formation of bonds between hydrogen and the transition and inner-transition metals and elements of group zero. This pattern is repeat- ed across the periodic system until all possible combinations of the elements have been treated. This plan allows most reaction topics to be included in the sequence where appropriate. Reaction types that do not arise from the system- atics of the plan are brought together in the concluding chapters on oxidative addition and reductive elimination, insertions and their reverse, electron trans- fer and electrochemistry, photochemical and other energized reactions, oligo- merization and polymerization, inorganic and bioinorganic catalysis and the formation of intercalation compounds and ceramics.
The project has engaged a large number of the most able inorganic chem- ists as Editorial Advisors creating overall policy, as Editorial Consultants de- signing detailed plans for the subsections of the work, and as authors whose expertise has been crucial for the quality of the treatment. The conception of the series and the details of its technical realization were the subject of careful planning for several years. The distinguished chemists who form the Editorial Advisory Board have devoted themselves to this exercise, reflecting the great importance of the project.
It was a consequence of the systematics of the overall plan that publica- tion of a volume had to await delivery of its very last contribution. Thus was the defect side of the genius of the system revealed, as the excruciating process of extracting the rate-limiting manuscripts began. Intense editorial effort was
xx i
xxii Preface to the Series
required in order to bring forth the work in a timely way. The production process had to be designed so that the insertion of new material was possible up to the very last stage, enabling authors to update their pieces with the lat- est developments. The publisher supported the cost of a computerized biblio- graphic search of the literature and a second one for updating.
Each contribution has been subjected to an intensive process of scientific and linguistic editing in order to homogenize the numerous individual pieces, as well as to provide the highest practicable density of information. This had several important consequences. First, virtually all semblances of the authors’ individual styles have been excised. Second, it was learned during the editorial process that greater economy of language could be achieved by dropping con- ventionally employed modifiers (such as very) and eliminating italics used for emphasis, quotation marks around nonquoted words, or parentheses around phrases, the result being a gain in clarity and readability. Because the series focuses on the chemistry rather than the chemical literature, the need to tell who has reported what, how and when can be considered of secondary impor- tance. This has made it possible to bring all sentences describing experiments into the present tense. Information on who published what is still to be found in the reference lists. A further consequence is that authors have been bur- dened neither with identifying leading practitioners, nor with attributing prior- ity for discovery, a job that taxes even the talents of professional historians of science. The authors’ task then devolved to one of describing inorganic chemi- cal reactions, with emphasis on synthetic utility, yield, economy, availability of starting materials, purity of product, specificity, side reactions, etc.
The elimination of the names of people from the text is by far the most controversial feature. Chemistry is plagued by the use of nondescriptive names in place of more expository terms. We have everything from Abegg’s rule, Adkin’s catalyst, Admiralty brass, Alfven number, the Amadori rearrange- ment and Adurssov oxidation to the Zdanovskii law, Zeeman effect, Zincke cleavage and Zinin reduction. Even well-practiced chemists cannot define these terms precisely except for their own areas of specialty, and no single source exists to serve as a guide. Despite these arguments, the attempt to replace names of people by more descriptive phrases was met in many cases by a warmly negative reaction by our colleague authors, notwithstanding the obvi- ous improvements wrought in terms of lucidity, freedom from obscurity and obfuscation and, especially, ease of access to information by the outsider or student.
Further steps toward universality are taken by the replacement of element and compound names wherever possible by symbols and formulas, and by adding to data in older units their recalculated SI equivalents. The usefulness of the reference sections has been increased by giving journal-title abbrevia- tions according to the Chemical Abstracts Service Source Index, by listing in each reference all of its authors and by accompanying references to patents and journals that may be difficult to access by their Chemical Abstracts cita-
Preface to the Series xxiii
tions. Mathematical signs and common abbreviations are employed to help condense prose and a glossary of the latter is provided in each volume. Dan- gerous or potentially dangerous procedures are highlighted in safety notes printed in boldface type.
The organization of the material should become readily apparent from an examination of the headings listed in the table of contents. Combining the words constituting the headings, starting with the major heading (one digit) and continuing through the major chapter heading (two digits), division head- ing (three digits), section heading (four digits) to the subsection heading (five digits), reveals at once the subject of a “slice” of the plan. Each slice is a self- contained unit. It includes its own list of references and provides definitions of unusual terms that may be used in it. The reader, therefore, through the table of contents alone, can in most instances quickly reach the desired material and derive the information wanted.
In addition there is for each volume an author index (derived from the lists of references) and a subject index that lists compound classes, methods, techniques, apparatus, effects and other phenomena. An index of empirical formulas is also provided. Here in each formula the element symbols are ar- ranged in alphabetical order except that c, or C and H if present, always come first. Moreover, each empirical formula is permuted successively. Each permuted formula is placed in its alphabetical position and cross referenced to the original formula. Therefore, the number of appearances that an empirical formula makes in the index equals the number of its elements. By this proce- dure all compounds containing a given element come together in one place in the index. Each original empirical formula is followed by a linearized structur- al formula and keywords describing the context in which the compound is dis- cussed. All indexes refer the user to subsection rather than page number.
Because the choice of designations of groups in the periodic table is cur- rently in a state of flux, it was decided to conform to the practice of several leading inorganic texts. To avoid confusion an appropriately labeled periodic table is printed on the back endpaper.
From the nature of the work it is obvious that probably not more than two persons will ever read it entire: myself and the publisher’s copy editor, Dr. Lindsay S. Ardwin. She, as well as Ms. Mary C. Stradner, Production Manager of VCH Publishers, are to be thanked for their unflagging devotion to the highest editorial standards. The original conception for this series was the brainchild of Dr. Hans F. Ebel, Director of the Editorial Department of VCH Verlagsgesellschaft in Weinheim, Federal Republic of Germany, who also played midwife at the birth of the plan of these reaction volumes with my former mentor, Professor Alan G. MacDiarmid of the University of Pennsyl- vania, and me in attendance, during the Anaheim, California, American Chemical Society Meeting in the Spring of 1978. Much of what has finally emerged is the product of the inventiveness and imagination of Professor Helmut Grunewald, President of VCH Verlagsgesellschaft. It is a pleasure to
xxiv Preface to the Series
acknowledge that I have learned much from him during the course of our as- sociation. Ms. Nancy L. Burnett is to be thanked for typing everything that had to do with the series from its inception to this time. Directing an opera- tion of this magnitude without her help would have been unimaginable. My wife Rose stood by with good cheer while two rooms of our home filled up with 10,OOO manuscript pages, their copies and attendant correspondence.
Finally, and most important, an enormous debt of gratitude toward all our authors is to be recorded. These experts were asked to prepare brief sum- maries of their knowledge, ordered in logical sequence by our plan. In addi- tion, they often involved themselves in improving the original conception by recommending further refinements and elaborations. The plan of the work as it is being published can truly be said to be the product of the labors of the advisors and consultants on the editorial side as well as the many, many au- thors who were able to augment more general knowledge with their own de- tailed information and ideas. Because of the unusually strict requirements of the series, authors had not only to compose their pieces to fit within narrowly constrained limits of space, format and scope, but after delivery to a short deadline were expected to stand by while an intrusive editorial process homog- enized their own prose styles out of existence and shrank the length of their expositions. These long-suffering colleagues had then to endure the wait for the very last manuscript scheduled for their volume to be delivered so that their work could be published, often after a further diligent search of the liter- ature to insure that the latest discoveries were being cited and that claims for facts now proved false were eliminated. To these co-workers (270 for the reac- tion volumes alone), from whom so much was demanded but who continued to place their knowledge and talents unstintingly at the disposal of the proj- ect, we dedicate this series.
J. J. ZUCKERMAN Norman, Oklahoma
July 4, 1985
The scientific community is appreciative of the JJZ vision for a systematic inorganic chemistry. Many of the contributions had been edited prior to his death; therefore, his precise syntax will remain an important part of the series.
A.P. HAGEN Norman, Oklahoma
June 1, 1990
Editorial Consultants to the Series
Professor H.R. Allcock Pennsylvania State University
Professor J.S. Anderson University of Aberystwyth
Professor F.C. Anson California Institute of Technology
Dr. M.G. Barker University of Nottingham
Professor D.J. Cardin Trinity College
Professor M.H. Chisholm Indiana University
Professor C. Cros Laboratoire de Chemie du Solide du
C.N.R.S.
Dr. B. Darriet Laboratoire de Chemie du Solide du
C.N.R.S.
Professor E.A.V. Ebsworth University of Edinburgh
Professor J.J. Eisch State University of New York at
Binghamton
Professor J.R. Etourneau Laboratoire de Chemie du Solide du
C.N.R.S.
Professor G.L. Geoffroy Pennsylvania State University
Professor L.S. Hegedus Colorado State University
Professor W.L. Jolly University of California at Berkeley
Professor C.B. Meyer University of Washington
Professor H. Noth Universitiit Munchen
Professor H. Nowotny University of Connecticut
Dr. G.W. Parshall E.I. du Pont de Nemours
Professor M. Pouchard Laboratoire de Chemie du Solide du
C.N.R.S.
Professor J. Rouxel Laboratoire de Chimie Minirale au
C.N.R.S.
xxv
xxvi
Professor R. Schmutzler Technische Universitat Braunschweig
Editorial Consultants to the Series
Dr. N. Sutin Brookhaven National Laboratory
Professor A.W. Searcy University of California at Berkeley
Professor R.A. Walton Purdue University
Professor D. Seyferth Dr. J.H. Wernick Massachusetts Institute of Bell Laboratories
Technology
Contributors to Volume 17
Professor H. R. Allcock Department of Chemistry Pennsylvania State University University Park, Pennsylvania 16802
(Sections 15.1.1, 15.1.2, 15.2.11)
Professor Dr. J. 0. Besenhard Anorganisch-Chemisches Institut Westfalische Wilhelms-Universitat
4400 Munster, BRD Miinster
(Sections 16.4.2.5,- 16.4.2.8)
Professor R. K. Bunting Department of Chemistry Illinois State University Normal, Illinois 61761-6901
(Sections 15.2.5, 15.2.6)
Professor T. Chivers Department of Chemistry The University of Calgary Alberta, T2N 1N4 Canada
(Section 15.2.12)
Dr. C. E. Carraher, Jr. Department of Chemistry Florida Atlantic University Boca Raton, Florida 33431
(Sections 15.1.13, 15.2.14)
Dr. C. Cros Laboratoire de Chemie du Solide du
CNRS 351, cours de la Liberation 33405 Talence, Cedex
(Sections 16.2.1- 16.2.3)
Dr. J. P. Doumerc Laboratoire de Chemie du Solide du
Universite de Bordeaux I 33405 Talence, Cedex
CNRS
(Section 16.3.2)
Dr. L. B. Ebert Corporate Research Exxon Research and Engineering
Clinton Township Rt 22 East Annandale, New Jersey 08801
(Sections 16.4.1-16.4.2.1)
Company
Professor J. P. Francois Department of Chemistry Limburgs Universitair Centrum 3610 Diepenbeek, Belgium
(Sections 15.2.1, 15.2.2)
Dr. C. L. Frye Health & Environmental Sciences Dow Corning Corporation Midland, Michigan 48686-0994
(Section 15.2.8)
Dr. D. Gubrard Laboratoire de Chimie du Solide
Universite de Nancy I
Vandoeuvse les Nancy Cedex
Mineral
B.P. 239-54506
(Section 16.4.2.4)
xxvii
xxviii Contributors to Volume 17
Professor A. Herold Laboratoire de Chimie du Solide
Universitk de Nancy I
Vandoeuvse les Nancy Cedex (Sections 16.4.2.2- 16.4.2.4)
Mineral
B.P. 239-54506
Professor B. Raveau Laboratoire de Cristallographie et
Chimie du Solide Universite de Caen 14032 Caen, Cedex
(Section 16.3.1)
Professor Dr. U. Klingebiel Institut fur Anorganische Chemie
Tammannstr. 4 3400 Gottingen, BRD
der Universitat Gottingen
(Section 15.2.9)
Dr. P. Lagrange Laboratoire de Chemie du Solide
Universite de Nancy I
Vandoeuvse les Nancy Cedex
Mineral
B.P. 239-54506
(Section 16.4.2.2.2)
dr. ir. C. H. Massen Department of Physics Eindhoven University of Technology 5600 Eindhoven, The Netherlands
(Sections 15.2.1, 15.2.2)
Professer T. P. Onak Department of Chemistry and
California State University, Los
Los Angeles, California 90032
Biochemistry
Angeles
(Section 15.2.7)
Prof. J. A. Poulis Department of Physics Eindhoven University of Technology 5600 Eindhoven, The Netherlands
(Sections 15.2.1, 15.2.2)
Professor A. L. Rheingold Department of Chemistry University of Delaware Newark, Delaware 19716
(Section 15.2.3)
Professor J. Rouxel Laboratoire de Chimie des Solides Institut de Physique et Chimie des
Universite de Nantes 44072 Nantes, Cedex
(Section 16.4.3)
Materiaux
Dr. R. Setton Centre de Recherche sur les Solides
B Organisation Cristalline Imparfaite, CNRS
45071 Orleans, Cedex 2 (Section 16.4.2.3)
Dr. L. C. van Poucke Department of Chemistry Limburgs Universitair Centrum 5600 Eindhoven, The Netherlands
(Sections 15.2.1, 15.2.2)
Professor J. R. Van Wazer Department of Chemistry Vanderbilt University Nashville, Tennessee 37235
(Sections 15.1.3, 15.2.10)
Dr. R. West Department of Chemistry University of Wisconsin Madison, Wisconsin 53706
(Section 15.2.4)
