ADVANCED INORGANIC CHEMISTRY A Comprehensive Text F. ALBERT COTTON ROBERT A. WELCH DISTINGUISHED PROFESSOR OF CHEMISTRY TEXAS A AND M UNIVERSITY COLLEGE STATION, TEXAS, USA’.* and GEOFFREY WILKINSON SIR EDWARD FRANKLAND PROFESSOR OF INORGANIC CHEMISTRY IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY UNIVERSITY OF LONDON, ENGLAND Fourth Edition, completely revised from the original literature A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS NEW YORK + CHICHESTER + BRISBANE + TORONTO407th Copyright © 1980 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada, Reproduction or translation of any pa¥ of this work beyond that permitted by Sections 107 and 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data Cotton, Frank Albert, 1930- ‘Advanced inorganic chemistry. “A Wiley-Interscience publication.” Includes index. 1. Chemistry, Inorganic. 1. Wilkinson, Geoffrey, 1921- joint author. _II. Title. QDIS1.2.C68 1980 54679-22506 ISBN 0-471-02775-8 Printed in the United States of America 10987654321 — AS 26 /Preface to the Fourth Edition It is remarkable how the subject of inorganic chemistry has not only grown but changed in form and emphasis since the early 1970s. In this fourth edition we have made major alterations in the arrangement of our material in an effort to reflect these changes. The main purpose of our book has not changed. It is to provide the student, or other reader, with the knowledge necessary to read with comprehension the con- temporary research literature in inorganic chemistry and certain areas of or- ganometallic chemistry. We have, as usual, also updated our coverage of all topics to include developments published as late as the first half of 1979. This, too, has entailed a significant in- crease in the amount of factual material. To keep the size of the book from getting out of hand we have omitted still more of the relatively elementary material included in earlier editions. There are now a number of more elementary textbooks, including our own Basic Inorganic Chemistry, where elementary topics are fully covered. For this reason we believe that the absence of this material here is pedagogically acceptable. We again wish to thank all of those who have been kind enough to give us con- structive suggestions and insight into fields where they are experts and we are not. We continue to be receptive to sucl contributions. F. ALBERT COTTON GEOFFREY WILKINSON College Station, Texas, USA London, England January 1980Preface to the First Edition It is now a truism that, in recent years, inorganic chemistry has experienced an impressive renaissance. Academic and industrial research in inorganic chemistry is flourishing, and the output of research papers and reviews is growing exponen- ly. In spite of this interest, however, there has been no comprehensive textbook on inorganic chemistry at an advanced level incorporating the many new chemical developments, particularly the more recent theoretical advances in the interpretation of bonding and reactivity in inorganic compounds. It is the aim of this book, which is based on courses given by the authors over the past five to ten years, to fill this need. It is our hope that it will provide a sound basis in contemporary inorganic chemistry for the new generation of students and will stimulate their interest in a field in which trained personnel are still exceedingly scarce in both academic and industrial laboratories. The content of this book, which encompasses the chemistry of all of the chemical elements and their compounds, including interpretative discussion in the light of the latest advances in structural chemistry, general valence theory, and, particularly, ligand field theory, provides a reasonable achievement for students at the B.Sc. honors level in British universities and at the senior year or first year graduate level in American universities. Our experience is that a course of about eighty lectures is desirable as a guide to the study of this material. We are indebted to several of our colleagues, who have read sections of the manuscript, for their suggestions and criticism. It is, of course, the authors alone who are responsible for any errors or omissions in the final draft. We also thank the various authors and editors who have so kindly given us permission to reproduce diagrams from their papers: specific acknowledgements are made in the text. We sincerely appreciate the secretarial assistance of Miss C. M. Ross and Mrs. A. B. Blake in the preparation of the manuscript. F, A. COTTON G. WILKINSON Cambridge, Massachusetts London, England viiContents PART ONE Introductory Topics 1. Nonmolecular Solids 2, Symmetry and Structure 3. Introduction to Ligands and Complexes 4. Classification of Ligands by Donor Atoms 5. Stereochemistry and Bonding in Main Group Compounds PART TWO Chemistry of the Main Group Elements 6. Hydrogen 7, The Group I Elements: Li, Na, K, Rb, Cs 8. Beryllium and the Group II Elements: Mg, Ca, Sr, Ba, Ra 9. Boron 10. The Group II Elements: Al, Ga, In, TI 11. Carbon 12. The Group IV Elements: Si, Ge, Sn, Pb 13. Nitrogen 14. The Group V Elements: P, As, Sb, Bi 15, Oxygen 16. The Group VI Elements: S, Se, Te, Po 17. The Halogens: F, Cl, Br, I, At 18. The Noble Gases 19. Zine, Cadmium, and Mercury 28 61 107 195 215 253 an 289 326 352 374 407 438 502 542 577 589x CONTENTS PART THREE Chemistry of the Transition Elements 20. The Transition Elements and the Electronic Structures of Their Compounds 21. The Elements of the First Transition Series . Titanium, 692 . Vanadium, 708 . Chromium, 719 . Manganese, 736 Iron, 749 Cobalt, 766 Nickel, 783 Copper, 798 e Elements of the Second and Third Transition Series . Zirconium and Hafnium, 824 Niobium and Tantalum, 831 Molybdenum and Tungsten, 844 . Technetium and Rhenium, 883 The Platinum Metals, 901 Ruthenium and Osmium, 912 Rhodium and Iridium, 934 . Palladium and Platinum, 950 Silver and Gold, 966 23. The Lanthanides; also Scandium and Yttrium 24, The Actinide Elements 22. FmMO™MOOP> STO ™MIOw> 5 s gms PART FOUR Special Topics 25, Metal Carbonyls and Other Complexes with -Acceptor Ligands 26. Metal-to-Metal Bonds and Metal Atom Clusters 27. Transition Metal Compounds with Bonds to Hydrogen and Carbon 28, Reaction Mechanisms and Molecular Rearrangements in Complexes 29, Transition Metal to Carbon Bonds in Synthesis 30. Transition Metal to Carbon Bonds in Catalysis 31. Bioinorganic Chemistry Appendices 1. Units, Fundamental Constants, and Conversion Factors 619 689 822 981 1005 1049 1080 1113 1183 1234 1265 1310 1347CONTENTS 2. Ionization Enthalpies of the Atoms 3. Enthalpies of Electron Attachment for Atoms 4. Atomic Orbitals 5. The Quantum States Derived from Electronic Configurations 6. Magnetic Properties of Chemical Compounds Index xi 1349 1351 1351 1354 1359 1367Abbreviations in Common Use 1. Chemicals, Ligands, Radicals, etc. Ac acetyl, CH;CO acac acetylacetonate anion acacH acetylacetone AIBN azoisobutyronitrile am ammonia (or occasionally an amine) Ar aryl or arene (ArH) aq aquated, H,O ATP adenosine triphosphate 9-BBN 9-borabicyclo[3,3,1]nonane bipy 2,2’-dipyridine, or bipyridine Bu butyl (superscript n, i, s or t, normal, iso, secondary or tertiary butyl) Bz benzyl COD orcod —_cycloocta-1,5-diene COT or cot cyclooctatetraene Cp cyclopentadienyl, CsHs cy cyclohexyl depe 1,2-bis(diethylphosphino)ethane depm 1,2-bis(diethylphosphino) methane diars o-phenylenebisdimethylarsine, o-CeHa(AsMe2)2 dien diethylenetriamine, HXN(CH2CH,NH)2H diglyme diethyleneglycoldimethylether, CH30(CH2CH20).CH3 diop {[2,2-dimethyl-1 ,3-dioxolan-4,5-diyl)bis(methylene) ]bis(diphen- ylphosphine)} diphos any chelating diphosphine, but usually 1,2- bis(diphenylphosphino)ethane, dppe DME dimethoxyethane DMF ordmf —_N,N’-dimethylformamide, HCONMe dmg dimethylglyoximate anion dmgH> dimethylglyoxime dmpe 1,2-bis(dimethylphosphino)ethane DMSO or dimethylsulfoxide, MezSO dmso xiiixiv dppe DPPH dppm EDTAHs EDTAHS, en Et Fe Fp glyme hfa HMPA L M Me Mes Megtren NBD or nbd NBS np? np} NTAH3 OAc Ox Pe Ph phen pn PNP (= np?) pp? PPNt+ Pr py pz QAS QP R Re Ss sal salzen or salen ABBREVIATIONS IN COMMON USE 1,2-bis(diphenylphosphino)ethane diphenylpicrylhydrazyl bis(diphenylphosphino)methane electrophile or element ethylenediaminetetraacetic acid anions of EDTAH4 ethylenediamine, H2NCH2CH2NH2 ethyl ferrocenyl Fe(CO)2Cp ethyleneglycoldimethylether, CH;0CH2CH,OCH3 hexafluoroacetylacetonate anion hexamethylphosphoric triamide, OP(NMe)3 ligand central (usually metal) atom in compound methyl mesityl tris-(2-dimethylaminoethyl)amine, N(CH)CH,NMe)3 norbornadiene N-bromosuccinimide Bis-(2-diphenylphosphinoethyl)amine, HN(CH2CH2PPh»)2 Tris-(2-diphenylphosphinoethyl)amine, N(CHxCH>PPh2)3 nitrilotriacetic acid, N(CH2COOH)3 acetate anion oxalate ion, C,0j- phthalocyanine phenyl, CeHs 1,10-phenanthroline propylenediamine (1,2-diaminopropane) Bis-(2-diphenylphosphinoethyl)amine, HN(CH2CH2PPh»)2 Tris-(2-diphenylphosphinoethyl)phosphine, P(CH2CHPPh2)3 [(Ph3P)2N]* propyl (superscripts, m or i) pyridine pyrazolyl Tris-(2-diphenylarsinophrnyl)arsine, As(o-CsH4AsPhy)3 Tris-(2-diphenylphosphinopheny!) phosphine, P(o-CgH4PPha)3 alkyl (preferably) or aryl group Perfluoro alkyl group solvent salicylaldehyde bis-salicylaldehydeethylenediimineTAN TAP TAS TCNE TCNQ terpy TFA THF or thf TMED tn TPN (= np3) TPP tren trien triphos TSN TSP TSeP TTA x ABBREVIATIONS IN COMMON USE xv Tris-(2-diphenylarsinoethyl)amine, N(CH2CH2AsPh))3 Tris-(3)dimethylarsinopropyl)phosphine, P(CH2CH2CH>AsMez)3 Bis-(3-dimethylarsinopropyl)methylarsine, * MeAs(CH2CH2CH2AsMe2)2 tetracyanoethylene 7,7,8,8-tetracyanoquinodimethane terpyridine trifluoroacetic acid tetrahydrofuran N,N,N’,N’-tetramethylethylenediamine 1,3-diaminopropane(trimethylenediamine) Tris-(2-diphenylphosphinoethyl)amine, N(CH2CH2PPh2)3 meso-tetraphenylporphyrin Tris-(2-aminoethyl)amine, N(CH2CH2NH2)3 Triethylenetetraamine, (CH2NHCHCH,NH?)> 1,1,1-tris(diphenylphosphinomethyl)ethane Tris-(2-methylthiomethy!)amine, N(CH»CH2SMe)3 Tris-(2-methylthiophenyl)phosphine, P(o-CsH4SMe)3 Tris-(2-methylselenophenyl)phosphine, P(o-CsH4SeMe)3 thenoyltrifluoroacetone, Cs H3SCPCH2CPCF3 halogen or pseudohalogen 2. Miscellaneous A AOM asym bee BM b.p. cep CFSE CFT CIDNP cm! CT d d- ESCA esr or epr eV Ft & Angstrom unit, 107! m angular overlap model asymmetric or antisymmetric body centered cubic Bohr magneton boiling point cubic close packed crystal field stabilization energy crystal field theory chemically induced dynamic nuclear polarization wave number charge transfer decomposes dextorotatory electron spectroscopy for chemical analysis electron spin (or paramagnetic) resonance electron volt Fourier transform (for nmr) g-valuesxvi (g) A hep HOMO Hz ICCC ir TUPAC Ie (O} LCAO. LFSE LFT LUMO MO MOSE mp. nmr P.E. R (s) SCE SCF SCF-Xa-SW Sp or spy str sub sym tbp SREZT™N SEC a ABBREVIATIONS IN COMMON USE gaseous state Planck’s constant hexagonal close packed highest occupied molecular orbital hertz, sec“! International Coordination Chemistry Conference infrared International Union of Pure and Applied Chemistry levorotatory liquid state linear combination of atomic orbitals ligand field stabilization energy ligand field theory lowest unoccupied molecular orbital molecular orbital molecular orbital stabilization energy melting point nuclear magnetic resonance photoelectron (spectroscopy) gas constant solid state saturated calomel electrode self consistent field self-consistent field, Xa, scattered wave (form of MO theory) square pyramid(al) vibrational stretching mode sublimes symmetrical trigonal bipyramid(al) lattice energy ultraviolet valence bond atomic number molar extinction coefficient frequency (cm! or Hz) magnetic moment in Bohr magnetons magnetic susceptibility Weiss constantADVANCED INORGANIC CHEMISTRY A Comprehensive Text FOURTH EDITION1 INTRODUCTORY TOPICSCHAPTER ON Nonmolecular Solids 1-1. Introductory Remarks Inorganic chemistry deals with substances having virtually every known type of physical and structural characteristic. It is not, therefore, easy to decide where to begin a book that will, in the end, have had something to say about many of them. There is no uniquely logical or convenient approach. No matter what order of topics is chosen, there are bound to be some carts before horses, since many facets of the subject interrelate in such a way that neither can be considered as simply prereq- uisite to the other. We begin this edition with a discussion of substances that exist in the solid state as extended arrays rather than molecular units. Although there are doubtless some arguments for not starting a book this way, we have several reasons for doing so. There are a great many important substances that are nonmolecular. Most of the elements themselves are nonmolecular. Thus more than half the elements are metals in which close-packed arrays of atoms are held together by delocalized electrons, while others, such as carbon, silicon, germanium, red and black phos- phorus, and boron involve infinite networks of more localized bonds. There are also many compounds, such as SiOz and SiC, in which the array is held together by localized heteropolar bonds. The degree of polarity varies, of course, and this class of substances grades off toward the limiting case of the ionic arrays in which there are well-defined ions held together principally by the Coulombic forces between those of opposite charge. There are also solids that consist neither of small, well-defined molecules nor of well-ordered infinite arrays of atoms; examples are the glasses and polymers, which, for reasons of space, are not explicitly discussed here. It is, of course, true that most molecular substances form a crystalline solid phase; but because of the relatively weak intermolecular interactions, crystallinity is usually of little chemical importance, though, of course, of enormous practical significance in that it facili- 34 INTRODUCTORY TOPICS tates the investigation of molecular structures, namely, by X-ray crystallog- raphy. Finally, we note that the area of materials science, which is a marriage of applied chemistry and applied physics, deals to a considerable extent with inorganic ma- terials: semiconductors, superconductors, ceramics, refractory compounds, alloys, and so on. Virtually all these are substances with nonmolecular structures. 1-2. Close Packing of Spheres The packing of spherical atoms or ions in such a way that the greatest number oc- cupy each unit of volume is one of the most fundamental structural patterns of Nature. It is seen in its simplest form in the solid noble gases, where spherical atoms are concerned, in a variety of ionic oxides and halides, where small cations can be considered to occupy interstices in a close-packed array of the larger spherical anions, and in metals where close-packed arrays of metal ions are permeated by a cloud of delocalized electrons binding them together. All close-packed arrangements are built by stacking of close-packed layers of the type shown in Fig. 1-1a; it should be evident that this is the densest packing arrangement in two dimensions. Two such layers may be brought together as shown Fig. 1-1. (a) One close-packed layer of spheres. (b) Two close-packed layers showing how tetrahedral (A, A’) and octahedral (B) interstices are formed,NONMOLECULAR SOLIDS 5 fo) (v) Fig. 1-2. (a) The stacking of close-packed layers in the ABC pat closest packing cep. (b) Another view of the cep pattern, emphasi rn that on repetition, gives cubic its cubic symmetry. in Fig. 1-1b, spheres of one layer resting in the declivities of the other; this is the densest packing arrangement of the two layers. It will be noted that between the two layers there exist interstices of two types: tetrahedral and octahedral. When we come to add a third layer to the two already stacked, two possibilities arise. The third layer can be placed so that its atoms lie directly over those of the first layer, or with a displacement relative to the first layer, as in Fig. 1-2a. These two stacking arrangements may be denoted ABA and ABC, respectively. Each may be continued in an ordered fashion so as to obtain Hexagonal close packing (hcp): ABABAB . Cubic close packing (cep): ABCABCABC. .. It is immediately obvious that the hcp arrangement does indeed have hexagonal symmetry, but the cubic symmetry of what has been designated cep may be less evident. Figure 1-2b provides another perspective, which emphasizes the cubic symmetry; it shows that the close-packed layers lie perpendicular to body diagonals of the cube. Moreover, the cubic unit cell is not primitive but face centered. There are, of course, an infinite number of stacking sequences possible within the definition of close packing, all of them, naturally, having the same packing density. The hep and cep sequences are those of maximum simplicity and symmetry. Some of the more complex sequences are actually encountered in Nature, though far less often than the two just described. In any close-packed arrangement, each atom has twelve nearest neighbors, six surrounding it in its own close-packed layer, three above and three below this layer. In the Acp structure each layer is a plane of symmetry and the set of nearest neighbors of each atom has D3, symmetry. In ccp the set of nearest neighbors has D3q symmetry. (See Section 2-4 for definition of these symbols.) 1-3. Metals It is evident, even on the most casual inspection, that metals have many physical Properties quite different from those of other solid substances. Although there are