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This book has established itself as a leading textbook in the subject by offering a fresh and exciting approach to the teaching of modern inorganic chemistry. It gives a clear introduction to key principles with strong coverage of descriptive chemistry of the elements. Special selected topics chapters are included, covering inorganic kinetics and mechanism, catalysis, solid state chemistry and bioinorganic chemistry.
A new full-colour text design and three-dimensional illustrations bring inorganic chemistry to life. Topic boxes have been used extensively throughout the book to relate the chemistry described in the text to everyday life, the chemical industry, environmental issues and legislation, and natural resources.
Teaching aids throughout the text have been carefully designed to help students learn effectively. The many worked examples take students through each calculation or exercise step by step, and are followed by related self-study exercises tackling similar problems with answers to help develop their confidence. In addition, end-of-chapter problems reinforce learning and develop subject
knowledge and skills. Definitions boxes and end-of-chapter checklists provide excellent revision aids, while further reading suggestions, from topical articles to recent
literature papers, will encourage students to explore topics in more depth.
Catherine E. Housecroft is Professor of Chemistry at the University of Basel, Switzerland. She is the author of a number of textbooks and has extensive teaching
experience in the UK, Switzerland, South Africa and the USA. Alan G. Sharpe is a Fellow of Jesus College, University of Cambridge, UK and has had many years of experience teaching inorganic chemistry to undergraduates
S E C O N D E D I T I O N
INORGANIC
CHEMISTRY
INORGANIC CHEMIS TR Y
S E C O N D E D I T I O N
New to this edition
• Many more self-study exercises have been introduced throughout the book with the aim of making stronger connections between descriptive chemistry and underlying principles.
• Additional ‘overview problems’ have been added to the end-of-chapter problem sets.
• The descriptive chemistry has been updated, with many new results from the literature being included.
• Chapter 4 – Bonding in polyatomic molecules, has been rewritten with greater emphasis on the use of group theory for the derivation of ligand group orbitals and orbital symmetry labels.
• There is more coverage of supercritical fluids and ‘green’ chemistry.
• The new full-colour text design enhances the presentation of the many molecular structures and 3-D images.
Supporting this edition
• Companion website featuring multiple- choice questions and rotatable 3-D molecular structures, available at
www.pearsoned.co.uk/housecroft. For full information including details of lecturer material see the Contents list inside the book.
• A Solutions Manual, written by Catherine E. Housecroft, with detailed solutions to all end-of-chapter problems within the text is available for purchase separately ISBN 0131 39926 8.
CHEMISTRY
CATHERINE E. HOUSECROFT AND ALAN G. SHARPE
C A THERINE E. HOUSECR OFT
AND ALAN G. SHARPE
S E C O N D E D I T I O N
For additional learning resources visit:
www.pearsoned.co.uk/housecroft Cover illustration by Gary Thompson
Visit the Inorganic Chemistry, second edition Companion Website at
www.pearsoned.co.uk/housecroft to find valuable student learning material including:
. Multiple choice questions to help test your learning . Web-based problems for Chapter 3
. Rotatable 3D structures taken from the book
. Interactive Periodic Table
Pearson Education Limited Edinburgh Gate
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Essex CM20 2JE England
and Associated Companies throughout the world Visit us on the World Wide Web at:
www.pearsoned.co.uk First edition 2001 Second edition 2005
#Pearson Education Limited 2001, 2005
The rights of Catherine E. Housecroft and Alan G. Sharpe to be identified as the authors of this Work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without either the prior written permission of the publisher or a licence permitting restricted copying in the United Kingdom issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP.
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The use of any trademark in this text does not vest in the author or publisher any trademark ownership rights in such trademarks, nor does the use of such trademarks imply any affiliation with or endorsement of this book by such owners.
ISBN 0130-39913-2
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress 10 9 8 7 6 5 4 3 2
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Typeset in 912/12 pt Times by 60
Printed by Ashford Colour Press Ltd., Gosport
Contents
Preface to the second edition xxxi
Preface to the first edition xxiii
1 Some basic concepts 1
1.1 Introduction 1
Inorganic chemistry: it is not an isolated branch of chemistry 1
The aims of Chapter 1 1
1.2 Fundamental particles of an atom 1
1.3 Atomic number, mass number and isotopes 2
Nuclides, atomic number and mass number 2
Relative atomic mass 2
Isotopes 2
1.4 Successes in early quantum theory 3
Some important successes of classical quantum theory 4
Bohr’s theory of the atomic spectrum of hydrogen 5
1.5 An introduction to wave mechanics 6
The wave-nature of electrons 6
The uncertainty principle 6
The Schro¨dinger wave equation 6
1.6 Atomic orbitals 9
The quantum numbers n, l and ml 9
The radial part of the wavefunction, RðrÞ 10
The radial distribution function, 4r2RðrÞ2 11
The angular part of the wavefunction, Að; Þ 12
Orbital energies in a hydrogen-like species 13
Size of orbitals 13
The spin quantum number and the magnetic spin quantum number 15
The ground state of the hydrogen atom 16
1.7 Many-electron atoms 16
The helium atom: two electrons 16
Ground state electronic configurations: experimental data 16
Penetration and shielding 17
1.8 The periodic table 17
1.9 The aufbau principle 21
Ground state electronic configurations 21
Valence and core electrons 22
Diagrammatic representations of electronic configurations 22
1.10 Ionization energies and electron affinities 23
Ionization energies 23
Electron affinities 25
1.11 Bonding models: an introduction 26
A historical overview 26
Lewis structures 26
1.12 Homonuclear diatomic molecules: valence bond (VB) theory 27
Uses of the term homonuclear 27
Covalent bond distance, covalent radius and van der Waals radius 27
The valence bond (VB) model of bonding in H2 27
The valence bond (VB) model applied to F2, O2and N2 28 1.13 Homonuclear diatomic molecules: molecular orbital (MO) theory 29
An overview of the MO model 29
Molecular orbital theory applied to the bonding in H2 29
The bonding in He2, Li2and Be2 31
The bonding in F2and O2 32
What happens if the s–p separation is small? 33
1.14 The octet rule 36
1.15 Electronegativity values 36
Pauling electronegativity values, P 37
Mulliken electronegativity values, M 37
Allred–Rochow electronegativity values, AR 38
Electronegativity: final remarks 38
1.16 Dipole moments 39
Polar diatomic molecules 39
Molecular dipole moments 40
1.17 MO theory: heteronuclear diatomic molecules 41
Which orbital interactions should be considered? 41
Hydrogen fluoride 42
Carbon monoxide 42
1.18 Isoelectronic molecules 43
1.19 Molecular shape and the VSEPR model 43
Valence-shell electron-pair repulsion theory 43
Structures derived from a trigonal bipyramid 47
Limitations of VSEPR theory 48
1.20 Molecular shape: geometrical isomerism 48
Square planar species 48
Octahedral species 48
Trigonal bipyramidal species 49
High coordination numbers 49
Double bonds 49
2 Nuclear properties 53
2.1 Introduction 53
2.2 Nuclear binding energy 53
Mass defect and binding energy 53
The average binding energy per nucleon 54
2.3 Radioactivity 55
Nuclear emissions 55
Nuclear transformations 55
The kinetics of radioactive decay 56
Units of radioactivity 57
2.4 Artificial isotopes 57
Bombardment of nuclei by high-energy a-particles and neutrons 57
Bombardment of nuclei by ‘slow’ neutrons 57
2.5 Nuclear fission 58
The fission of uranium-235 58
The production of energy by nuclear fission 60
Nuclear reprocessing 61
2.6 Syntheses of transuranium elements 61
2.7 The separation of radioactive isotopes 62
Chemical separation 62
The Szilard–Chalmers effect 62
2.8 Nuclear fusion 62
2.9 Applications of isotopes 63
Infrared (IR) spectroscopy 63
Kinetic isotope effects 64
Radiocarbon dating 64
Analytical applications 65
2.10 Sources of2H and13C 65
Deuterium: electrolytic separation of isotopes 65
Carbon-13: chemical enrichment 65
2.11 Multinuclear NMR spectroscopy in inorganic chemistry 67 Which nuclei are suitable for NMR spectroscopic studies? 68
Chemical shift ranges 68
Spin–spin coupling 69
Stereochemically non-rigid species 72
Exchange processes in solution 73
2.12 Mo¨ssbauer spectroscopy in inorganic chemistry 73
The technique of Mo¨ssbauer spectroscopy 73
What can isomer shift data tell us? 75
Contents vii
3 An introduction to molecular symmetry 79
3.1 Introduction 79
3.2 Symmetry operations and symmetry elements 79
Rotation about an n-fold axis of symmetry 80
Reflection through a plane of symmetry (mirror plane) 80 Reflection through a centre of symmetry (inversion centre) 82 Rotation about an axis, followed by reflection through a plane perpendicular
to this axis 82
Identity operator 82
3.3 Successive operations 84
3.4 Point groups 85
C1point group 85
C1vpoint group 85
D1h point group 85
Td, Oh or Ihpoint groups 86
Determining the point group of a molecule or molecular ion 86
3.5 Character tables: an introduction 89
3.6 Why do we need to recognize symmetry elements? 90
3.7 Infrared spectroscopy 90
How many vibrational modes are there for a given molecular species? 90 Selection rule for an infrared active mode of vibration 91 Linear (D1h or C1v) and bent (C2v) triatomic molecules 92
XY3molecules with D3hor C3vsymmetry 92
XY4molecules with Td or D4hsymmetry 93
Observing IR spectroscopic absorptions: practical problems 94
3.8 Chiral molecules 95
4 Bonding in polyatomic molecules 100
4.1 Introduction 100
4.2 Valence bond theory: hybridization of atomic orbitals 100
What is orbital hybridization? 100
spHybridization: a scheme for linear species 101
sp2Hybridization: a scheme for trigonal planar species 102 sp3Hybridization: a scheme for tetrahedral and related species 103
Other hybridization schemes 104
4.3 Valence bond theory: multiple bonding in polyatomic molecules 105
C2H4 105
HCN 105
BF3 106
4.4 Molecular orbital theory: the ligand group orbital approach and
application to triatomic molecules 107
Molecular orbital diagrams: moving from a diatomic to polyatomic species 107
MO approach to the bonding in linear XH2: symmetry matching by inspection 107 MO approach to bonding in linear XH2: working from molecular symmetry 109
A bent triatomic: H2O 109
4.5 Molecular orbital theory applied to the polyatomic molecules BH3,
NH3 and CH4 112
BH3 112
NH3 113
CH4 115
A comparison of the MO and VB bonding models 116
4.6 Molecular orbital theory: bonding analyses soon become complicated 117 4.7 Molecular orbital theory: learning to use the theory objectively 119
-Bonding in CO2 119
[NO3] 120
SF6 120
Three-centre two-electron interactions 123
A more advanced problem: B2H6 124
5 Structures and energetics of metallic and ionic solids 131
5.1 Introduction 131
5.2 Packing of spheres 131
Cubic and hexagonal close-packing 131
The unit cell: hexagonal and cubic close-packing 132
Interstitial holes: hexagonal and cubic close-packing 133 Non-close-packing: simple cubic and body-centred cubic arrays 134 5.3 The packing-of-spheres model applied to the structures of elements 134
Group 18 elements in the solid state 134
H2and F2in the solid state 134
Metallic elements in the solid state 134
5.4 Polymorphism in metals 136
Polymorphism: phase changes in the solid state 136
Phase diagrams 136
5.5 Metallic radii 136
5.6 Melting points and standard enthalpies of atomization of metals 137
5.7 Alloys and intermetallic compounds 139
Substitutional alloys 139
Interstitial alloys 139
Intermetallic compounds 140
5.8 Bonding in metals and semiconductors 141
Electrical conductivity and resistivity 141
Band theory of metals and insulators 141
The Fermi level 142
Band theory of semiconductors 143
Contents ix
5.9 Semiconductors 143
Intrinsic semiconductors 143
Extrinsic (n- and p-type) semiconductors 143
5.10 Sizes of ions 144
Ionic radii 144
Periodic trends in ionic radii 145
5.11 Ionic lattices 146
The rock salt (NaCl) lattice 148
The caesium chloride (CsCl) lattice 149
The fluorite (CaF2) lattice 149
The antifluorite lattice 149
The zinc blende (ZnS) lattice: a diamond-type network 149
The b-cristobalite (SiO2) lattice 150
The wurtzite (ZnS) structure 151
The rutile (TiO2) structure 151
The CdI2and CdCl2lattices: layer structures 151
The perovskite (CaTiO3) lattice: a double oxide 152
5.12 Crystal structures of semiconductors 152
5.13 Lattice energy: estimates from an electrostatic model 152
Coulombic attraction within an isolated ion-pair 152
Coulombic interactions in an ionic lattice 153
Born forces 153
The Born–Lande´ equation 154
Madelung constants 154
Refinements to the Born–Lande´ equation 155
Overview 155
5.14 Lattice energy: the Born–Haber cycle 155
5.15 Lattice energy: ‘calculated’ versus ‘experimental’ values 156
5.16 Applications of lattice energies 157
Estimation of electron affinities 157
Fluoride affinities 157
Estimation of standard enthalpies of formation and disproportionation 157
The Kapustinskii equation 158
5.17 Defects in solid state lattices: an introduction 158
Schottky defect 158
Frenkel defect 158
Experimental observation of Schottky and Frenkel defects 159
6 Acids, bases and ions in aqueous solution 162
6.1 Introduction 162
6.2 Properties of water 162
Structure and hydrogen bonding 162
The self-ionization of water 163
Water as a Brønsted acid or base 163
6.3 Definitions and units in aqueous solution 165
Molarity and molality 165
Standard state 165
Activity 165
6.4 Some Brønsted acids and bases 166
Carboxylic acids: examples of mono-, di- and polybasic acids 166
Inorganic acids 167
Inorganic bases: hydroxides 167
Inorganic bases: nitrogen bases 168
6.5 The energetics of acid dissociation in aqueous solution 169
Hydrogen halides 169
H2S, H2Se and H2Te 170
6.6 Trends within a series of oxoacids EOn(OH)m 170
6.7 Aquated cations: formation and acidic properties 171
Water as a Lewis base 171
Aquated cations as Brønsted acids 172
6.8 Amphoteric oxides and hydroxides 173
Amphoteric behaviour 173
Periodic trends in amphoteric properties 173
6.9 Solubilities of ionic salts 174
Solubility and saturated solutions 174
Sparingly soluble salts and solubility products 174
The energetics of the dissolution of an ionic salt: solGo 175 The energetics of the dissolution of an ionic salt: hydration of ions 176
Solubilities: some concluding remarks 177
6.10 Common-ion effect 178
6.11 Coordination complexes: an introduction 178
Definitions and terminology 178
Investigating coordination complex formation 179
6.12 Stability constants of coordination complexes 180
Determination of stability constants 182
Trends in stepwise stability constants 182
Thermodynamic considerations of complex formation: an introduction 182 6.13 Factors affecting the stabilities of complexes containing only
monodentate ligands 186
Ionic size and charge 186
Hard and soft metal centres and ligands 187
7 Reduction and oxidation 192
7.1 Introduction 192
Oxidation and reduction 192
Oxidation states 192
Stock nomenclature 193
Contents xi
7.2 Standard reduction potentials, Eo, and relationships between Eo,
Goand K 193
Half-cells and galvanic cells 193
Defining and using standard reduction potentials, Eo 195 Dependence of reduction potentials on cell conditions 197 7.3 The effect of complex formation or precipitation on Mzþ/M reduction
potentials 199
Half-cells involving silver halides 199
Modifying the relative stabilities of different oxidation states of a metal 200
7.4 Disproportionation reactions 203
Disproportionation 203
Stabilizing species against disproportionation 203
7.5 Potential diagrams 203
7.6 Frost–Ebsworth diagrams 205
Frost–Ebsworth diagrams and their relationship to potential diagrams 205
Interpretation of Frost–Ebsworth diagrams 206
7.7 The relationships between standard reduction potentials and some
other quantities 208
Factors influencing the magnitudes of standard reduction potentials 208
Values of fGo for aqueous ions 209
7.8 Applications of redox reactions to the extraction of elements from their
ores 210
Ellingham diagrams 210
8 Non-aqueous media 214
8.1 Introduction 214
8.2 Relative permittivity 214
8.3 Energetics of ionic salt transfer from water to an organic solvent 215
8.4 Acid–base behaviour in non-aqueous solvents 216
Strengths of acids and bases 216
Levelling and differentiating effects 217
‘Acids’ in acidic solvents 217
Acids and bases: a solvent-oriented definition 217
8.5 Self-ionizing and non-ionizing non-aqueous solvents 217
8.6 Liquid ammonia 218
Physical properties 218
Self-ionization 218
Reactions in liquid NH3 218
Solutions of s-block metals in liquid NH3 219
Redox reactions in liquid NH3 221
8.7 Liquid hydrogen fluoride 221
Physical properties 221
Acid–base behaviour in liquid HF 221
Electrolysis in liquid HF 222
8.8 Sulfuric acid 222
Physical properties 222
Acid–base behaviour in liquid H2SO4 223
8.9 Fluorosulfonic acid 223
Physical properties 223
Superacids 224
8.10 Bromine trifluoride 224
Physical properties 224
Behaviour of fluoride salts and molecular fluorides in BrF3 225
Reactions in BrF3 225
8.11 Dinitrogen tetraoxide 225
Physical properties 225
Reactions in N2O4 226
8.12 Ionic liquids 227
Molten salt solvent systems 227
Ionic liquids at ambient temperatures 227
Reactions in and applications of molten salt/ionic liquid media 229
8.13 Supercritical fluids 230
Properties of supercritical fluids and their uses as solvents 230 Supercritical fluids as media for inorganic chemistry 232
9 Hydrogen 236
9.1 Hydrogen: the simplest atom 236
9.2 The Hþand H ions 236
The hydrogen ion (proton) 236
The hydride ion 237
9.3 Isotopes of hydrogen 237
Protium and deuterium 237
Deuterated compounds 237
Tritium 238
9.4 Dihydrogen 238
Occurrence 238
Physical properties 238
Synthesis and uses 238
Reactivity 242
9.5 Polar and non-polar EH bonds 244
9.6 Hydrogen bonding 244
The hydrogen bond 244
Trends in boiling points, melting points and enthalpies of vaporization for
p-block binary hydrides 246
Contents xiii
Infrared spectroscopy 246
Solid state structures 247
Hydrogen bonding in biological systems 250
9.7 Binary hydrides: classification and general properties 251
Classification 251
Interstitial metal hydrides 251
Saline hydrides 251
Molecular hydrides and complexes derived from them 253
Polymeric hydrides 254
Intermediate hydrides 255
10 Group 1: the alkali metals 257
10.1 Introduction 257
10.2 Occurrence, extraction and uses 257
Occurrence 257
Extraction 257
Major uses of the alkali metals and their compounds 259
10.3 Physical properties 259
General properties 259
Atomic spectra and flame tests 260
Radioactive isotopes 261
NMR active nuclei 261
10.4 The metals 261
Appearance 261
Reactivity 261
10.5 Halides 263
10.6 Oxides and hydroxides 264
Oxides, peroxides, superoxides, suboxides and ozonides 264
Hydroxides 265
10.7 Salts of oxoacids: carbonates and hydrogencarbonates 265 10.8 Aqueous solution chemistry including macrocyclic complexes 267
Hydrated ions 267
Complex ions 268
10.9 Non-aqueous coordination chemistry 271
11 The group 2 metals 275
11.1 Introduction 275
11.2 Occurrence, extraction and uses 275
Occurrence 275
Extraction 276
Major uses of the group 2 metals and their compounds 277
11.3 Physical properties 278
General properties 278
Flame tests 279
Radioactive isotopes 279
11.4 The metals 279
Appearance 279
Reactivity 279
11.5 Halides 280
Beryllium halides 280
Halides of Mg, Ca, Sr and Ba 282
11.6 Oxides and hydroxides 283
Oxides and peroxides 283
Hydroxides 285
11.7 Salts of oxoacids 286
11.8 Complex ions in aqueous solution 287
Aqua species of beryllium 287
Aqua species of Mg2þ, Ca2þ, Sr2þand Ba2þ 288
Complexes with ligands other than water 288
11.9 Complexes with amido or alkoxy ligands 288
11.10 Diagonal relationships between Li and Mg, and between Be and Al 288
Lithium and magnesium 289
Beryllium and aluminium 290
12 The group 13 elements 293
12.1 Introduction 293
12.2 Occurrence, extraction and uses 293
Occurrence 293
Extraction 293
Major uses of the group 13 elements and their compounds 295
12.3 Physical properties 296
Electronic configurations and oxidation states 296
NMR active nuclei 299
12.4 The elements 299
Appearance 299
Structures of the elements 300
Reactivity 301
12.5 Simple hydrides 301
Neutral hydrides 301
The½MH4ions 305
12.6 Halides and complex halides 307
Boron halides: BX3and B2X4 307
Al(III), Ga(III), In(III) and Tl(III) halides and their complexes 309
Lower oxidation state Al, Ga, In and Tl halides 311
Contents xv
12.7 Oxides, oxoacids, oxoanions and hydroxides 313
Boron oxides, oxoacids and oxoanions 313
Aluminium oxides, oxoacids, oxoanions and hydroxides 316
Oxides of Ga, In and Tl 317
12.8 Compounds containing nitrogen 317
Nitrides 317
Ternary boron nitrides 318
Molecular species containing B–N or B–P bonds 319
Molecular species containing group 13 metal–nitrogen bonds 321 12.9 Aluminium to thallium: salts of oxoacids, aqueous solution chemistry
and complexes 322
Aluminium sulfate and alums 322
Aqua ions 322
Redox reactions in aqueous solution 322
Coordination complexes of the M3þions 323
12.10 Metal borides 324
12.11 Electron-deficient borane and carbaborane clusters: an introduction 326
Boron hydrides 326
13 The group 14 elements 338
13.1 Introduction 338
13.2 Occurrence, extraction and uses 338
Occurrence 338
Extraction and manufacture 339
Uses 339
13.3 Physical properties 342
Ionization energies and cation formation 342
Some energetic and bonding considerations 343
NMR active nuclei 344
Mo¨ssbauer spectroscopy 344
13.4 Allotropes of carbon 345
Graphite and diamond: structure and properties 345
Graphite: intercalation compounds 345
Fullerenes: synthesis and structure 348
Fullerenes: reactivity 349
Carbon nanotubes 353
13.5 Structural and chemical properties of silicon, germanium, tin and lead 353
Structures 353
Chemical properties 353
13.6 Hydrides 354
Binary hydrides 354
Halohydrides of silicon and germanium 356
13.7 Carbides, silicides, germides, stannides and plumbides 357
Carbides 357
Silicides 358
Germides, stannides and plumbides 358
13.8 Halides and complex halides 361
Carbon halides 361
Silicon halides 363
Halides of germanium, tin and lead 364
13.9 Oxides, oxoacids and hydroxides 365
Oxides and oxoacids of carbon 365
Silica, silicates and aluminosilicates 369
Oxides, hydroxides and oxoacids of germanium, tin and lead 373
13.10 Silicones 376
13.11 Sulfides 377
13.12 Cyanogen, silicon nitride and tin nitride 379
Cyanogen and its derivatives 379
Silicon nitride 380
Tin(IV) nitride 381
13.13 Aqueous solution chemistry and salts of oxoacids of germanium,
tin and lead 381
14 The group 15 elements 385
14.1 Introduction 385
14.2 Occurrence, extraction and uses 386
Occurrence 386
Extraction 387
Uses 387
14.3 Physical properties 389
Bonding considerations 390
NMR active nuclei 391
Radioactive isotopes 391
14.4 The elements 392
Nitrogen 392
Phosphorus 392
Arsenic, antimony and bismuth 393
14.5 Hydrides 394
Trihydrides, EH3(E¼ N, P, As, Sb and Bi) 394
Hydrides E2H4(E¼ N, P, As) 397
Chloramine and hydroxylamine 398
Hydrogen azide and azide salts 399
14.6 Nitrides, phosphides, arsenides, antimonides and bismuthides 401
Nitrides 401
Phosphides 402
Arsenides, antimonides and bismuthides 402
Contents xvii
14.7 Halides, oxohalides and complex halides 403
Nitrogen halides 403
Oxofluorides and oxochlorides of nitrogen 405
Phosphorus halides 406
Phosphoryl trichloride, POCl3 408
Arsenic and antimony halides 409
Bismuth halides 411
14.8 Oxides of nitrogen 412
Dinitrogen monoxide, N2O 412
Nitrogen monoxide, NO 412
Dinitrogen trioxide, N2O3 413
Dinitrogen tetraoxide, N2O4, and nitrogen dioxide, NO2 414
Dinitrogen pentaoxide, N2O5 415
14.9 Oxoacids of nitrogen 415
Hyponitrous acid, H2N2O2 415
Nitrous acid, HNO2 415
Nitric acid, HNO3, and its derivatives 416
14.10 Oxides of phosphorus, arsenic, antimony and bismuth 417
Oxides of phosphorus 418
Oxides of arsenic, antimony and bismuth 419
14.11 Oxoacids of phosphorus 419
Phosphinic acid, H3PO2 419
Phosphonic acid, H3PO3 420
Hypophosphoric acid, H4P2O6 420
Phosphoric acid, H3PO4, and its derivatives 421
14.12 Oxoacids of arsenic, antimony and bismuth 422
14.13 Phosphazenes 424
14.14 Sulfides and selenides 426
Sulfides and selenides of phosphorus 426
Arsenic, antimony and bismuth sulfides 428
14.15 Aqueous solution chemistry 428
15 The group 16 elements 432
15.1 Introduction 432
15.2 Occurrence, extraction and uses 432
Occurrence 432
Extraction 433
Uses 433
15.3 Physical properties and bonding considerations 434
NMR active nuclei and isotopes as tracers 437
15.4 The elements 437
Dioxygen 437
Ozone 438
Sulfur: allotropes 439
Sulfur: reactivity 440
Selenium and tellurium 441
15.5 Hydrides 442
Water, H2O 442
Hydrogen peroxide, H2O2 442
Hydrides H2E (E¼ S, Se, Te) 445
Polysulfanes 445
15.6 Metal sulfides, polysulfides, polyselenides and polytellurides 446
Sulfides 446
Polysulfides 446
Polyselenides and polytellurides 447
15.7 Halides, oxohalides and complex halides 448
Oxygen fluorides 448
Sulfur fluorides and oxofluorides 448
Sulfur chlorides and oxochlorides 450
Halides of selenium and tellurium 451
15.8 Oxides 453
Oxides of sulfur 453
Oxides of selenium and tellurium 456
15.9 Oxoacids and their salts 457
Dithionous acid, H2S2O4 457
Sulfurous and disulfurous acids, H2SO3and H2S2O5 457
Dithionic acid, H2S2O6 458
Sulfuric acid, H2SO4 459
Fluoro- and chlorosulfonic acids, HSO3F and HSO3Cl 461
Polyoxoacids with SOS units 461
Peroxosulfuric acids, H2S2O8and H2SO5 461
Thiosulfuric acid, H2S2O3, and polythionates 461
Oxoacids of selenium and tellurium 462
15.10 Compounds of sulfur and selenium with nitrogen 462
Sulfur–nitrogen compounds 462
Tetraselenium tetranitride 464
15.11 Aqueous solution chemistry of sulfur, selenium and tellurium 464
16 The group 17 elements 468
16.1 Introduction 468
Fluorine, chlorine, bromine and iodine 468
Astatine 469
16.2 Occurrence, extraction and uses 469
Occurrence 469
Extraction 470
Uses 471
16.3 Physical properties and bonding considerations 471
NMR active nuclei and isotopes as tracers 473
Contents xix
16.4 The elements 474
Difluorine 474
Dichlorine, dibromine and diiodine 475
Charge transfer complexes 475
Clathrates 477
16.5 Hydrogen halides 477
16.6 Metal halides: structures and energetics 478
16.7 Interhalogen compounds and polyhalogen ions 479
Interhalogen compounds 479
Bonding in½XY2ions 482
Polyhalogen cations 482
Polyhalide anions 483
16.8 Oxides and oxofluorides of chlorine, bromine and iodine 483
Oxides 483
Oxofluorides 484
16.9 Oxoacids and their salts 485
Hypofluorous acid, HOF 485
Oxoacids of chlorine, bromine and iodine 485
16.10 Aqueous solution chemistry 488
17 The group 18 elements 492
17.1 Introduction 492
17.2 Occurrence, extraction and uses 493
Occurrence 493
Extraction 493
Uses 493
17.3 Physical properties 494
NMR active nuclei 495
17.4 Compounds of xenon 496
Fluorides 496
Chlorides 498
Oxides 499
Oxofluorides 499
Other compounds of xenon 499
17.5 Compounds of krypton and radon 501
18 Organometallic compounds of s- and p-block elements 503
18.1 Introduction 503
18.2 Group 1: alkali metal organometallics 504
18.3 Group 2 organometallics 507
Beryllium 507
Magnesium 509
Calcium, strontium and barium 510
18.4 Group 13 511
Boron 511
Aluminium 511
Gallium, indium and thallium 514
18.5 Group 14 518
Silicon 518
Germanium 520
Tin 521
Lead 524
Coparallel and tilted C5-rings in group 14 metallocenes 526
18.6 Group 15 527
Bonding aspects and E¼E bond formation 527
Arsenic, antimony and bismuth 527
18.7 Group 16 530
Selenium and tellurium 530
19 d-Block chemistry: general considerations 535
19.1 Topic overview 535
19.2 Ground state electronic configurations 535
d-Block metals versus transition elements 535
Electronic configurations 536
19.3 Physical properties 536
19.4 The reactivity of the metals 538
19.5 Characteristic properties: a general perspective 538
Colour 538
Paramagnetism 539
Complex formation 539
Variable oxidation states 539
19.6 Electroneutrality principle 539
19.7 Coordination numbers 541
The Kepert model 541
Coordination number 2 543
Coordination number 3 543
Coordination number 4 543
Coordination number 5 544
Coordination number 6 544
Coordination number 7 545
Coordination number 8 546
Coordination number 9 547
Coordination numbers of 10 and above 547
Contents xxi
19.8 Isomerism in d-block metal complexes 547
Structural isomerism: ionization isomers 548
Structural isomerism: hydration isomers 548
Structural isomerism: coordination isomerism 549
Structural isomerism: linkage isomerism 549
Structural isomerism: polymerization isomerism 549
Stereoisomerism: geometrical isomers 549
Stereoisomerism: optical isomers 549
20 d-Block chemistry: coordination complexes 555
20.1 Introduction 555
High- and low-spin states 555
20.2 Bonding in d-block metal complexes: valence bond theory 555
Hybridization schemes 555
Applying VB theory 556
20.3 Crystal field theory 557
The octahedral crystal field 558
Crystal field stabilization energy: high- and low-spin octahedral complexes 560
Jahn–Teller distortions 561
The tetrahedral crystal field 562
The square planar crystal field 562
Other crystal fields 564
Crystal field theory: uses and limitations 564
20.4 Molecular orbital theory: octahedral complexes 564
Complexes with no metal–ligand -bonding 564
Complexes with metal–ligand -bonding 566
20.5 Ligand field theory 570
20.6 Electronic spectra 570
Spectral features 570
Selection rules 571
Electronic spectra of octahedral and tetrahedral complexes 574
Microstates 576
Tanabe–Sugano diagrams 577
20.7 Evidence for metal–ligand covalent bonding 578
The nephelauxetic effect 578
ESR spectroscopy 579
20.8 Magnetic properties 579
Magnetic susceptibility and the spin-only formula 579
Spin and orbital contributions to the magnetic moment 581
The effects of temperature on eff 583
Spin crossover 584
Ferromagnetism, antiferromagnetism and ferrimagnetism 584 20.9 Thermodynamic aspects: ligand field stabilization energies (LFSE) 585
Trends in LFSE 585
Lattice energies and hydration energies of Mnþions 586 Octahedral versus tetrahedral coordination: spinels 587
20.10 Thermodynamic aspects: the Irving–Williams series 587 20.11 Thermodynamic aspects: oxidation states in aqueous solution 588
21 d-Block metal chemistry: the first row metals 593
21.1 Introduction 593
21.2 Occurrence, extraction and uses 593
21.3 Physical properties: an overview 597
21.4 Group 3: scandium 597
The metal 597
Scandium(III) 598
21.5 Group 4: titanium 598
The metal 598
Titanium(IV) 598
Titanium(III) 601
Low oxidation states 601
21.6 Group 5: vanadium 602
The metal 602
Vanadium(V) 602
Vanadium(IV) 604
Vanadium(III) 605
Vanadium(II) 605
21.7 Group 6: chromium 606
The metal 606
Chromium(VI) 606
Chromium(V) and chromium(IV) 607
Chromium(III) 608
Chromium(II) 609
Chromium–chromium multiple bonds 610
21.8 Group 7: manganese 611
The metal 611
Manganese(VII) 612
Manganese(VI) 613
Manganese(V) 613
Manganese(IV) 613
Manganese(III) 614
Manganese(II) 616
21.9 Group 8: iron 617
The metal 617
Iron(VI), iron(V) and iron(IV) 617
Iron(III) 618
Iron(II) 622
21.10 Group 9: cobalt 624
The metal 624
Cobalt(IV) 624
Contents xxiii
Cobalt(III) 624
Cobalt(II) 627
21.11 Group 10: nickel 630
The metal 630
Nickel(IV) and nickel(III) 630
Nickel(II) 631
Nickel(I) 634
21.12 Group 11: copper 634
The metal 634
Copper(IV) and (III) 634
Copper(II) 635
Copper(I) 637
21.13 Group 12: zinc 639
The metal 639
Zinc(II) 640
22 d-Block metal chemistry: the second and third row metals 645
22.1 Introduction 645
22.2 Occurrence, extraction and uses 645
22.3 Physical properties 649
Effects of the lanthanoid contraction 649
Coordination numbers 649
NMR active nuclei 649
22.4 Group 3: yttrium 651
The metal 651
Yttrium(III) 651
22.5 Group 4: zirconium and hafnium 652
The metals 652
Zirconium(IV) and hafnium(IV) 652
Lower oxidation states of zirconium and hafnium 652
Zirconium clusters 653
22.6 Group 5: niobium and tantalum 654
The metals 654
Niobium(V) and tantalum(V) 654
Niobium(IV) and tantalum(IV) 656
Lower oxidation state halides 656
22.7 Group 6: molybdenum and tungsten 658
The metals 658
Molybdenum(VI) and tungsten(VI) 659
Molybdenum(V) and tungsten(V) 662
Molybdenum(IV) and tungsten(IV) 663
Molybdenum(III) and tungsten(III) 663
Molybdenum(II) and tungsten(II) 665
22.8 Group 7: technetium and rhenium 666
The metals 666
High oxidation states of technetium and rhenium: M(VII), M(VI) and M(V) 667
Technetium(IV) and rhenium(IV) 669
Technetium(III) and rhenium(III) 669
22.9 Group 8: ruthenium and osmium 671
The metals 671
High oxidation states of ruthenium and osmium: M(VIII), M(VII) and M(VI) 671
Ruthenium(V), (IV) and osmium(V), (IV) 673
Ruthenium(III) and osmium(III) 675
Ruthenium(II) and osmium(II) 676
Mixed-valence ruthenium complexes 678
22.10 Group 9: rhodium and iridium 679
The metals 679
High oxidation states of rhodium and iridium: M(VI) and M(V) 679
Rhodium(IV) and iridium (IV) 680
Rhodium(III) and iridium(III) 680
Rhodium(II) and iridium(II) 682
Rhodium(I) and iridium(I) 683
22.11 Group 10: palladium and platinum 684
The metals 684
The highest oxidation states: M(VI) and M(V) 684
Palladium(IV) and platinum(IV) 684
Palladium(III), platinum(III) and mixed-valence complexes 685
Palladium(II) and platinum(II) 686
22.12 Group 11: silver and gold 689
The metals 689
Gold(V) and silver(V) 690
Gold(III) and silver(III) 690
Gold(II) and silver(II) 691
Gold(I) and silver(I) 692
Gold(I) and silver(I) 694
22.13 Group 12: cadmium and mercury 694
The metals 694
Cadmium(II) 695
Mercury(II) 695
Mercury(I) 696
23 Organometallic compounds of d-block elements 700
23.1 Introduction 700
Hapticity of a ligand 700
23.2 Common types of ligand: bonding and spectroscopy 700
-Bonded alkyl, aryl and related ligands 700
Carbonyl ligands 701
Hydride ligands 702
Phosphine and related ligands 703
-Bonded organic ligands 704
Dinitrogen 706
Dihydrogen 707
23.3 The 18-electron rule 707
Contents xxv
23.4 Metal carbonyls: synthesis, physical properties and structure 709
Synthesis and physical properties 710
Structures 711
23.5 The isolobal principle and application of Wade’s rules 714 23.6 Total valence electron counts in d-block organometallic clusters 716
Single cage structures 717
Condensed cages 718
Limitations of total valence counting schemes 719
23.7 Types of organometallic reactions 719
Substitution of CO ligands 719
Oxidative addition 719
Alkyl and hydrogen migrations 720
b-Hydrogen elimination 721
a-Hydrogen abstraction 721
Summary 722
23.8 Metal carbonyls: selected reactions 722
23.9 Metal carbonyl hydrides and halides 723
23.10 Alkyl, aryl, alkene and alkyne complexes 724
-Bonded alkyl and aryl ligands 724
Alkene ligands 725
Alkyne ligands 726
23.11 Allyl and buta-1,3-diene complexes 727
Allyl and related ligands 727
Buta-1,3-diene and related ligands 728
23.12 Carbene and carbyne complexes 729
23.13 Complexes containing Z5-cyclopentadienyl ligands 730
Ferrocene and other metallocenes 731
ðZ5-CpÞ2Fe2ðCOÞ4and derivatives 732
23.14 Complexes containing Z6- and Z7-ligands 734
Z6-Arene ligands 734
Cycloheptatriene and derived ligands 735
23.15 Complexes containing the Z4-cyclobutadiene ligand 737
24 The f -block metals: lanthanoids and actinoids 741
24.1 Introduction 741
24.2 f -Orbitals and oxidation states 742
24.3 Atom and ion sizes 743
The lanthanoid contraction 743
Coordination numbers 743
24.4 Spectroscopic and magnetic properties 744 Electronic spectra and magnetic moments: lanthanoids 744
Luminescence of lanthanoid complexes 746
Electronic spectra and magnetic moments: actinoids 746
24.5 Sources of the lanthanoids and actinoids 747
Occurrence and separation of the lanthanoids 747
The actinoids 748
24.6 Lanthanoid metals 748
24.7 Inorganic compounds and coordination complexes of the lanthanoids 749
Halides 749
Hydroxides and oxides 750
Complexes of Ln(III) 750
24.8 Organometallic complexes of the lanthanoids 751
-Bonded complexes 751
Cyclopentadienyl complexes 753
Bis(arene) derivatives 755
Complexes containing the Z8-cyclooctatetraenyl ligand 755
24.9 The actinoid metals 755
24.10 Inorganic compounds and coordination complexes of thorium,
uranium and plutonium 756
Thorium 756
Uranium 757
Plutonium 758
24.11 Organometallic complexes of thorium and uranium 759
-Bonded complexes 759
Cyclopentadienyl derivatives 760
Complexes containing the Z8-cyclooctatetraenyl ligand 761
25 d-Block metal complexes: reaction mechanisms 764
25.1 Introduction 764
25.2 Ligand substitutions: some general points 764
Kinetically inert and labile complexes 764
Stoichiometric equations say nothing about mechanism 764
Types of substitution mechanism 765
Activation parameters 765
25.3 Substitution in square planar complexes 766
Rate equations, mechanism and the trans-effect 766
Ligand nucleophilicity 769
25.4 Substitution and racemization in octahedral complexes 769
Water exchange 770
The Eigen–Wilkins mechanism 772
Stereochemistry of substitution 774
Base-catalysed hydrolysis 774
Isomerization and racemization of octahedral complexes 776
Contents xxvii
25.5 Electron-transfer processes 777
Inner-sphere mechanism 777
Outer-sphere mechanism 779
26 Homogeneous and heterogeneous catalysis 786
26.1 Introduction and definitions 786
26.2 Catalysis: introductory concepts 786
Energy profiles for a reaction: catalysed versus non-catalysed 786
Catalytic cycles 787
Choosing a catalyst 788
26.3 Homogeneous catalysis: alkene (olefin) metathesis 789
26.4 Homogeneous catalysis: industrial applications 791
Alkene hydrogenation 791
Monsanto acetic acid synthesis 793
Tennessee–Eastman acetic anhydride process 794
Hydroformylation (Oxo-process) 795
Alkene oligomerization 797
26.5 Homogeneous catalyst development 797
Polymer-supported catalysts 797
Biphasic catalysis 798
d-Block organometallic clusters as homogeneous catalysts 799 26.6 Heterogeneous catalysis: surfaces and interactions with adsorbates 799
26.7 Heterogeneous catalysis: commercial applications 802
Alkene polymerization: Ziegler–Natta catalysis 802
Fischer–Tropsch carbon chain growth 803
Haber process 804
Production of SO3in the Contact process 805
Catalytic converters 805
Zeolites as catalysts for organic transformations: uses of ZSM-5 806 26.8 Heterogeneous catalysis: organometallic cluster models 807
27 Some aspects of solid state chemistry 813
27.1 Introduction 813
27.2 Defects in solid state lattices 813
Types of defect: stoichiometric and non-stoichiometric compounds 813
Colour centres (F-centres) 814
Thermodynamic effects of crystal defects 814
27.3 Electrical conductivity in ionic solids 815
Sodium and lithium ion conductors 815
d-Block metal(II) oxides 816
27.4 Superconductivity 817
Superconductors: early examples and basic theory 817
High-temperature superconductors 817
Superconducting properties of MgB2 819
Applications of superconductors 819
27.5 Ceramic materials: colour pigments 819
White pigments (opacifiers) 820
Adding colour 820
27.6 Chemical vapour deposition (CVD) 820
High-purity silicon for semiconductors 821
a-Boron nitride 821
Silicon nitride and carbide 821
III–V Semiconductors 822
Metal deposition 823
Ceramic coatings 824
Perovskites and cuprate superconductors 824
27.7 Inorganic fibres 826
Boron fibres 826
Carbon fibres 826
Silicon carbide fibres 827
Alumina fibres 827
28 The trace metals of life 830
28.1 Introduction 830
Amino acids, peptides and proteins: some terminology 830
28.2 Metal storage and transport: Fe, Cu, Zn and V 832
Iron storage and transport 832
Metallothioneins: transporting some toxic metals 835
28.3 Dealing with O2 837
Haemoglobin and myoglobin 837
Haemocyanin 839
Haemerythrin 841
Cytochromes P-450 843
28.4 Biological redox processes 843
Blue copper proteins 844
The mitochondrial electron-transfer chain 845
Iron–sulfur proteins 847
Cytochromes 851
28.5 The Zn2+ion: Nature’s Lewis acid 854
Carbonic anhydrase II 854
Carboxypeptidase A 855
Carboxypeptidase G2 858
Cobalt-for-zinc ion substitution 859
Contents xxix
Appendices 863
1 Greek letters with pronunciations 864
2 Abbreviations and symbols for quantities and units 865
3 Selected character tables 869
4 The electromagnetic spectrum 873
5 Naturally occurring isotopes and their abundances 875
6 Van der Waals, metallic, covalent and ionic radii for the s-, p- and
first row d-block elements 877
7 Pauling electronegativity values (P) for selected elements of the
periodic table 879
8 Ground state electronic configurations of the elements and
ionization energies for the first five ionizations 880
9 Electron affinities 883
10 Standard enthalpies of atomization (aHo) of the elements at 298 K 884
11 Selected standard reduction potentials (298 K) 885
Answers to non-descriptive problems 888
Index 905
Preface to the second edition
The second edition of Inorganic Chemistry is a natural progression from the first edition published in 2001. In this last text, we stated that our aim was to provide a single volume that gives a critical introduction to modern inorganic chemistry. Our approach to inorganic chemistry continues as before: we provide a foundation of physical inorganic principles and theory followed by descriptive chemistry of the elements, and a number of
‘special topics’ that can, if desired, be used for modular teaching. Boxed material has been used extensively to relate the chemistry described in the text to everyday life, the chemical industry, environmental issues and legislation, and natural resources.
In going from the first to second editions, the most obvious change has been a move from two to full colour. This has given us the opportunity to enhance the presentations of many of the molecular structures and 3D images. In terms of content, the descriptive chemistry has been updated, with many new results from the literature being included.
Some exciting advances have taken place in the past two to three years spanning small molecule chemistry (for example, the chemistry of [N5]þ), solid state chemistry (e.g.
the first examples of spinel nitrides) and bioinorganic systems (a landmark discovery is that of a central, 6-coordinate atom, probably nitrogen, at the centre of the FeMo- cofactor in nitrogenase). Other changes to the book have their origins in feedback from people using the text. Chapters 3 and 4 have been modified; in particular, the role of group theory in determining ligand group orbitals and orbital symmetry labels has been more thoroughly explored. However, we do not feel that a book, the prime purpose of which is to bring chemistry to a student audience, should evolve into a theoretical text. For this reason, we have refrained from an in-depth treatment of group theory. Throughout the book, we have used the popular ‘worked examples’ and
‘self-study exercises’ as a means of helping students to grasp principles and concepts.
Many more self-study exercises have been introduced throughout the book, with the aim of making stronger connections between descriptive chemistry and underlying principles. Additional ‘overview problems’ have been added to the end-of-chapter problem sets; in Chapter 3, a set of new problems has been designed to work in conjunction with rotatable structures on the accompanying website (www.pearsoned.
co.uk/housecroft).
Supplementary data accompanying this text include a Solutions Manual written by Catherine E. Housecroft. The accompanying website includes features for both students and lecturers and can be accessed from www.pearsoned.co.uk/housecroft.
The 3D-molecular structures the book have been drawn using atomic coordinates accessed from the Cambridge Crystallographic Data Base and implemented through the ETH in Zu¨rich, or from the Protein Data Bank (http://www/rcsb.org/pdb).
We are very grateful to many lecturers who have passed on their comments and criticisms of the first edition of Inorganic Chemistry. Some of these remain anonymous to us and can be thanked only as ‘the review panel set up by Pearson Education.’ In addition to those colleagues whom we acknowledged in the preface to the first edition, we are grateful to Professors Duncan Bruce, Edwin Constable, Ronald Gillespie, Robert Hancock, Laura Hughes, Todd Marder, Christian Reber, David Tudela and Karl Wieghardt, and Drs Andrew Hughes and Mark Thornton-Pett who provided us with a range of thought-provoking comments. We are, of course, indebted to the team at Pearson Education who have supported the writing project and have taken the manuscript and graphics files through to their final form and provided their expertise for the development of the accompanying website. Special thanks go to Bridget Allen,
Kevin Ancient, Melanie Beard, Pauline Gillett, Simon Lake, Mary Lince, Paul Nash, Abigail Woodman and Ros Woodward.
Having another inorganic chemist on-call in the house during the preparation of the book has been more than beneficial: one of us owes much to her husband, Edwin Constable, for his critical comments. His insistence that a PC should replace the long- serving series of Macs has proved a bonus for the production of artwork. Finally, two beloved feline companions have once again taken an active role (not always helpful) in the preparation of this text – Philby and Isis have a unique ability to make sure they are the centre of attention, no matter how many deadlines have to be met.
Catherine E. Housecroft (Basel) Alan G. Sharpe (Cambridge) March 2004
Online resources
Visit www.pearsoned.co.uk/housecroft to find valuable online resources Companion Website for students
. Multiple choice questions to help test your learning . Web-based problems for Chapter 3
. Rotatable 3D structures taken from the book . Interactive Periodic Table
For instructors . Guide for lecturers
. Rotatable 3D structures taken from the book . PowerPoint slides
Also: The Companion Website provides the following features:
. Search tool to help locate specific items of content
. E-mail results and profile tools to send results of quizzes to instructors . Online help and support to assist with website usage and troubleshooting
For more information please contact your local Pearson Education sales representative or visit www.pearsoned.co.uk/housecroft
Preface to the first edition
Inorganic Chemistry has developed from the three editions of Alan Sharpe’s Inorganic Chemistry and builds upon the success of this text. The aim of the two books is the same: to provide a single volume that gives a critical introduction to modern inorganic chemistry. However, in making the transition, the book has undergone a complete over- haul, not only in a complete rewriting of the text, but also in the general format, pedago- gical features and illustrations. These changes give Inorganic Chemistry a more modern feel while retaining the original characteristic approach to the discussions, in particular of general principles of inorganic chemistry. Inorganic Chemistry provides students with numerous fully-worked examples of calculations, extensive end-of-chapter problems, and ‘boxed’ material relating to chemical and theoretical background, chemical resources, the effects of chemicals on the environment and applications of inorganic chemicals. The book contains chapters on physical inorganic chemistry and descriptive chemistry of the elements. Descriptive chapters build upon the foundations laid in the earlier chapters.
The material is presented in a logical order but navigation through the text is aided by comprehensive cross-references. The book is completed by four ‘topic’ chapters covering inorganic kinetics, catalysis, aspects of the solid state and bioinorganic chemistry. Each chapter in the book ends with a summary and a checklist of new chemical terms. The reading lists contain suggestions both for books and articles in the current literature.
Additional information about websites of interest to readers of this book can be accessed via: http://www.booksites.net/housecroft
The content of all descriptive chemistry chapters contains up-to-date information and takes into account the results of the latest research; in particular, the chapters on organo- metallic chemistry of the s- and p-block and d-block elements reflect a surge in research interest in this area of chemistry. Another major development from Alan Sharpe’s original text has been to extend the discussion of molecular orbital theory, with an aim not only of introducing the topic but also showing how an objective (and cautious) approach can provide insight into particular bonding features of molecular species. Greater emphasis on the use of multinuclear NMR spectroscopy has been included; case studies introduce I >12nuclei and the observation of satellite peaks and applications of NMR spectroscopy are discussed where appropriate throughout the text. Appendices are included and are a feature of the book; they provide tables of physical data, selected character tables, and a list of abbreviations.
Answers to non-descriptive problems are included in Inorganic Chemistry, but a separate Solutions Manual has been written by Catherine Housecroft, and this gives detailed answers or essay plans for all end of chapter problems.
Most of the 3D-structural diagrams in the book have been drawn using Chem3D Pro.
with coordinates accessed from the Cambridge Crystallographic Data Base and imple- mented through the ETH in Zu¨rich. The protein structures in Chapter 28 have been drawn using Rasmol with data from the Protein Data Bank (http://www/rcsb.org/pdb).
Suggestions passed on by readers of Alan Sharpe’s Inorganic Chemistry have helped us to identify ‘holes’ and, in particular, we thank Professor Derek Corbridge. We gratefully acknowledge comments made on the manuscript by members of the panel of reviewers (from the UK, the Netherlands and the US) set up by Pearson Education. A number of colleagues have read chapters of the manuscript and their suggestions and criticisms have been invaluable: special thanks go to Professors Steve Chapman, Edwin Constable, Michael Davies and Georg Su¨ss-Fink, and Dr Malcolm Gerloch. We should also like to thank Dr Paul Bowyer for information on sulfur dioxide in wine production, and
Dr Bo Sundman for providing data for the iron phase-diagram. A text of this type cannot become reality without dedicated work from the publisher: from among those at Pearson Education who have seen this project develop from infancy and provided us with support, particular thanks go to Lynn Brandon, Pauline Gillett, Julie Knight, Paul Nash, Alex Seabrook and Ros Woodward, and to Bridget Allen and Kevin Ancient for tireless and dedicated work on the design and artwork.
One of us must express sincere thanks to her husband, Edwin Constable, for endless discussions and critique. Thanks again to two very special feline companions, Philby and Isis, who have sat, slept and played by the Macintosh through every minute of the writing of this edition – they are not always patient, but their love and affection is an integral part of writing.
Catherine E. Housecroft Alan G. Sharpe June 2000
The publishers are grateful to the following for permission to reproduce copyright maerial:
Professor B. N. Figgis for Figure 20.20 from Figgis, B. N. (1966) Introduction to Ligand Fields, New York: Interscience.
In some instances we have been unable to trace the owners of copyright material, and we would appreciate any information that would enable us to do so.
