Physical Inorganic Chemistry A Coordination Chemistry Approach

by Kettle, S. F. A.

ISBN13: 9780198504047

ISBN10: 0198504047

Format: Paperback

Pub. Date: 2000-04-13

Publisher(s): Oxford University Press

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Summary

Inorganic chemistry has in recent years been changing dramatically, withcoordination chemistry in particular undergoing a striking resurgence ofinterest. This has been fuelled by the growth in importance of metals inbiology and medicine, and by the new and explosive thrusts into inorganicmaterials. These changes mean that today's student of inorganic chemistry needsa greater knowledge and understanding of physical inorganic chemistry.Embracing such topics as bonding state chemistry and cluster chemistry, thediscipline underpins the whole of modern inorganic chemistry. This theme spansvirtually the whole of physical inorganic chemistry; and an important benefit ofthis approach is that the book doubles as a text on coordination chemistryitself. Physical Inorganic Chemistry is a an accessible, largelynon-mathematical text which bridges the gap between the relatively low-leveltreatments currently available and the specialists, research-level ones. Itprovides an account of the traditional areas of the subject, combining this withan introduction to important contemporary research areas, the whole viewed froman integrated theoretical perspective. Each chapter is self-contained, allowingmaximum flexibility in course-text use. '[This text] represents a wonderfulbridge for the student. It is designed as an intermediate-level that can serveboth as a user-friendly introduction to a large number of topics and techniquesof importance to the student of coordination and physical inorganic chemistry,and also as a springboard to more advanced texts and studies. It is written ina style that is appropriate for a teaching text, anticipating and answering thequestions that students will typically have on encountering the topic for thefirst time, and introduces a large number of theoretical, spectroscopic andphysicochemical techniques without sacrificing the more classical content of acoordination chemistry text. In this regard, it is a wonderful hybrid of theclassic and modern aspects of coordination and physical inorganic chemistry andis consequently an admirable text for the student of this area'.

Foreword

xiii

Preface

Introduction

(6)

Typical ligands, typical complexes

(17)

Classical ligands, classical complexes

(3)

Novel ligands, novel complexes

(11)

Some final comments

(3)

Nomenclature, geometrical structure and isomerism of coordination compounds

(27)

Nomenclature

(7)

Coordination numbers

(11)

Complexes with coordination numbers one, two or three

(1)

Complexes with coordination number four

(2)

Complexes with coordination number five

(3)

Complexes with coordination number six

(1)

Complexes with coordination number seven

(1)

Complexes with coordination number eight

(2)

Complexes with coordination number nine

(1)

Complexes of higher coordination number

(1)

What determines coordination number and geometry?

(1)

Isomerism in coordination compounds

(8)

Conformation isomerism

(1)

Geometrical isomerism

(1)

Coordination position isomerism

(1)

Coordination isomerism

(1)

Ionization isomerism

(1)

Hydrate isomerism

(1)

Linkage isomerism

(1)

Polymerization isomerism

(1)

Ligand isomerism

(1)

Optical isomerism

(1)

Structural and fluxional isomerism

(1)

Spin isomerism

(3)

Preparation of coordination compounds

(22)

Introduction

(1)

Preparative methods

(21)

Simple addition reactions

(2)

Substitution reactions

(4)

Oxidation-reduction reactions

(3)

Thermal dissociation reactions

(1)

Preparations in the absence of oxygen

(3)

Reactions of coordinated ligands

(3)

The trans effect

(1)

Other methods of preparing coordination compounds

(4)

Stability of coordination compounds

(22)

Introduction

(1)

Stability constants

(1)

Determination of stability constants

(5)

Stability correlations

(4)

Statistical and chelate effects

(5)

Solid complexes

(1)

Steric effects

(2)

Conclusions

(3)

Molecular orbital theory of transition metal complexes

(26)

Introduction

(2)

Octahedral complexes

(10)

Metal-ligand σ interactions

(6)

Metal-ligand π interactions

103

(4)

Tetrahedral complexes

107

(3)

Complexes of other geometries

110

(5)

Formal oxidation states

115

(2)

Experimental

117

(4)

Crystal field theory of transition metal complexes

121

(35)

Introduction

121

(1)

Symmetry and crystal field theory

122

(1)

Crystal field splittings

123

(7)

Weak field complexes

130

(6)

Strong field complexes

136

(7)

Intermediate field complexes

143

(5)

Non-octahedral complexes

148

(1)

Tetrahedral complexes

148

(2)

Square planar complexes

150

(2)

Other stereochemistries

152

(1)

Ligand field theory

153

(3)

Electronic spectra of transition metal complexes

156

(29)

Introduction

156

(1)

The electronic spectra of VIII and NiII complexes

157

(6)

Spin-forbidden transitions

163

(1)

Effect of spin-orbit coupling

164

(2)

Jahn-Teller effect

166

(4)

Band contours

170

(1)

Band intensities

171

(4)

Tetrahedral complexes

175

(1)

Complexes of other geometries

176

(2)

Charge-transfer spectra

178

(3)

Intervalence charge-transfer bands

181

(1)

Conclusions

182

(3)

Magnetic properties of transition metal complexes

185

(26)

Introduction

185

(2)

Classical magnetism

187

(2)

Orbital contribution to a magnetic moment

189

(2)

Spin contribution to a magnetic moment

191

(1)

Spin-orbit coupling

191

(1)

Low symmetry ligand fields

192

(1)

Experimental results

193

(2)

Orbital contribution reduction factor

195

(1)

An example

195

(6)

Spin-only equation

201

(2)

Magnetically non-dilute compounds

203

(5)

Spin equilibria

208

(3)

Beyond ligand field theory

211

(27)

Bonding in transition metal organometallic complexes

211

(4)

Metal-fullerene complexes

215

(5)

Ab initio and Xα methods

220

(2)

Semiempirical methods

222

(1)

Extended Huckel method

222

(4)

Angular overlap model

226

(1)

Three examples: ferrocene, hexacarbonylchromium and ethenetetracarbonyliron

227

(8)

Ferrocene

227

(2)

Hexacarbonylchromium

229

(3)

Ethenetetracarbonyliron

232

(3)

Final comments

235

(3)

f electron systems: the lanthanides and actinides

238

(31)

Introduction

238

(2)

Shapes of f orbitals

240

(3)

Electronic structure of the lanthanide and actinide ions

243

(4)

Spin-orbit coupling

247

(2)

Spin-orbit coupling in pictures

249

(5)

Excited states of f electron systems

254

(3)

Electronic spectra of f electron systems

257

(3)

Crystal fields and f → f intensities

260

(2)

f → d and charge-transfer transitions

262

(1)

Lanthanide luminescence

263

(2)

Magnetism of lanthanide and actinide ions

265

(2)

f orbital involvement in bonding

267

(2)

Other methods of studying coordination compounds

269

(34)

Introduction

269

(1)

Vibrational spectroscopy

270

(5)

Resonance Raman spectroscopy

275

(2)

Spectroscopic methods unique to optically active molecules

277

(4)

Nuclear spectroscopies

281

(7)

Nuclear magnetic resonance (NMR)

283

(2)

Nuclear quadrupole resonance (NQR)

285

(1)

Mossbauer spectroscopy

286

(2)

Electron paramagnetic (spin) resonance spectroscopy (EPR, ESR)

288

(3)

Photoelectron spectroscopy (PES)

291

(4)

Evidence for covalency in transition metal complexes

295

(1)

Molar conductivities

296

(1)

Cyclic voltammetry

297

(2)

X-ray crystallography

299

(2)

Conclusion

301

(2)

Thermodynamic and related aspects of ligand fields

303

(14)

Introduction

303

(1)

Ionic radii

303

(2)

Heats of ligation

305

(2)

Lattice energies

307

(1)

Site preference energies

308

(3)

Stability constants

311

(1)

Lanthanides

312

(2)

Molecular mechanics

314

(1)

Conclusions

315

(2)

Reaction kinetics of coordination compounds

317

(28)

Introduction

317

(3)

Electron-transfer reactions

320

(5)

Mechanisms of ligand substitution reactions: general considerations

325

(3)

Substitution reactions of square planar complexes

328

(3)

Substitution reactions of octahedral complexes

331

(4)

Base-catalysed hydrolysis of cobalt(III) ammine complexes

335

(2)

Mechanisms of ligand substitution reactions: postscript

337

(1)

Fluxional molecules

338

(1)

Photokinetics of inorganic complexes

339

(6)

Bonding in cluster compounds

345

(36)

Introduction

345

(1)

Bonding in P4 (and B4Cl4)

346

(7)

`Simple ammonia' model for P4

346

(2)

`Twisted ammonia' model for P4

348

(2)

Atomic orbital model for P4

350

(2)

Unity of the three models of P4 bonding

352

(1)

Wade's rules

353

(6)

Topological models

359

(3)

Free-electron models

362

(13)

Detailed calculations

375

(4)

Clusters and catalysis, a comment

379

(2)

Some aspects of bioinorganic chemistry

381

(26)

Introduction

381

(3)

Myoglobin and hemoglobin

384

(7)

Search for reaction intermediates

391

(2)

Peroxidases

393

(5)

Blue copper proteins

398

(3)

Nitrogen fixation

401

(2)

Protonation equilibria in bioinorganic systems

403

(4)

Introduction to the theory of the solid state

407

(25)

Introduction

407

(1)

Nodes, nodes and more nodes

408

(5)

Travelling waves and the Brillouin zone

413

(4)

Band structure

417

(5)

Fermi surface

422

(2)

Solid state and coordination compounds

424

(4)

Spectra of crystalline materials

428

(4)

Appendix 1 Conformation of chelate rings

432

(3)

Appendix 2 Valence shell electron pair repulsion (VSEPR) model

435

(5)

Appendix 3 Introduction to group theory

440

(5)

Appendix 4 Equivalence of dz2 and dx2-y2 in an octahedral ligand field

445

(1)

Appendix 5 Russell-Saunders coupling scheme

446

(3)

Appendix 6 Ligand σ group orbitals of an octahedral complex

449

(6)

Appendix 7 Tanabe-Sugano diagrams and some illustrative spectra

455

(4)

Appendix 8 Group theoretical aspects of band intensities in octahedral complexes

459

(3)

Appendix 9 Determination of magnetic susceptibilities

462

(4)

Appendix 10 Magnetic susceptibility of a tetragonally distorted t1/2g ion

466

(6)

Appendix 11 High temperature superconductors

472

(5)

Appendix 12 Combining spin and orbital angular momenta

477

(2)

Appendix 13 Bonding between a transition metal atom and a CnRn ring, n = 4, 5 and 6

479

(5)

Appendix 14 Hole-electron relationship in spin-orbit coupling

484

(3)

Index

487

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Physical Inorganic Chemistry A Coordination Chemistry Approach

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Physical Inorganic Chemistry A Coordination Chemistry Approach

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