Yves Jean - Molecular Orbitals of Transition Metal Complexes (793957)
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Molecular Orbitals of TransitionMetal ComplexesThis page intentionally left blankMolecular Orbitals of TransitionMetal ComplexesYves JeanLaboratoire de Chimie Physique,Université Paris-SudTranslated byColin MarsdenLaboratoire de Physique Quantique,Université Paul Sabatier,Toulouse13Great Clarendon Street, Oxford OX DPOxford University Press is a department of the University of Oxford.It furthers the University’s objective of excellence in research, scholarship,and education by publishing worldwide inOxford New YorkAuckland Bangkok Buenos Aires Cape Town ChennaiDar es Salaam Delhi Hong Kong Istanbul Karachi KolkataKuala Lumpur Madrid Melbourne Mexico City Mumbai NairobiSão Paulo Shanghai Taipei Tokyo TorontoOxford is a registered trade mark of Oxford University Pressin the UK and in certain other countriesPublished in the United Statesby Oxford University Press Inc., New YorkOriginal French edition:Les orbitales moléculaires dans les complexes ISBN 2 7302 1024 5© Editions de l’Ecole Polytechnique 2003English version © Oxford University Press 2005The moral rights of the authors have been assertedDatabase right Oxford University Press (maker)First published 2005All rights reserved.
No part of this publication may be reproduced,stored in a retrieval system, or transmitted, in any form or by any means,without the prior permission in writing of Oxford University Press,or as expressly permitted by law, or under terms agreed with the appropriatereprographics rights organization. Enquiries concerning reproductionoutside the scope of the above should be sent to the Rights Department,Oxford University Press, at the address aboveYou must not circulate this book in any other binding or coverand you must impose this same condition on any acquirerA catalogue record for this title is available from the British LibraryLibrary of Congress Cataloging in Publication Data(Data available)ISBN 0 19 853093 5 (Hbk)10 9 8 7 6 5 4 3 2 1Typeset by Newgen Imaging Systems (P) Ltd., Chennai, IndiaPrinted in Great Britainon acid-free paper byAntony Rowe, ChippenhamForewordWe are so divided.
By the formal structure of university instruction—organic chemistry, inorganic chemistry, physical chemistry. By theincredible and unnecessary specialization of our journals. The molecular bounty we have ourselves created seems simply overwhelming—nowonder we seek compartmentalization in self-protection: It is easy tosay, ‘I’m an expert in Field x. And while I will listen to a seminar in y or z(when I have time), please .
. . let me be happy just in keeping up withmy own field.’The dangers of specialization are obvious—inbreeding, lack of scope,a kind of rococo elaboration of chemical complexity within a field.And we know that new ideas often come from an almost metaphoricalimportation of a way of thinking or a technique from another area.Meanwhile, all along, nature persists in subverting the compartmentalizing simplicity of our minds.
Through enzymes whose seemingmagic is done by metal atoms and clusters at the active site, inorganicchemistry and biochemistry are rejoined. Transition metal carbidesput organic carbon into some most unusual, patently inorganic environments. And, beginning in 1950, the explosion in organometallicchemistry has given us an incredible riches of structures and reactions—from ferrocene to olefin metathesis, metal–metal multiple bonds, to−H activation, and remarkable olefin polymerization catalysts.
AllC−from a combination of inorganic and organic chemistry.Organometallic chemistry from its beginning also depended on,and also built, another bridge. This is to theoretical chemistry. Thefirst, rationalizing accounts of the electronic structure of ferroceneand the Dewar–Chatt–Duncanson picture of metal–olefin bondingwere followed by milestones such as the prediction of cyclobutadiene–iron tricarbonyl and Cotton’s beautiful elaboration of the idea of ametal–metal quadruple bond. The work of Leslie Orgel played a veryimportant role in those early days. There were fecund interactions allalong—compounds leading to calculations, and calculations pushingexperimentalists to make new molecules.
Often the theory was doneby the experimentalists themselves, for the best kind of theory (the onethat keeps the fertile dance of experiment moving) is a portable one. Aseasy to use molecular orbital theory, the theory of choice of the times,most certainly was and is.ForewordIt is hard to imagine a contemporary course in organometallicchemistry which does not contain a hefty, albeit qualitative component of molecular orbital theory.
Yves Jean (with François Volatron)earlier wrote a classic teaching text on the orbitals of organic molecules.Here he has applied his great pedagogical skills to the construction ofa beautifully thought through exposition of bonding in organometallic chemistry. Our undergraduate and graduate students will enjoy thisbook. And they, the chemists of the future, will use the knowledge gainedhere to enlarge our experience with new organometallic molecules,subverting once again the arbitrary division of organic and inorganicchemistry.
Molecules whose beauty and utility we still cannot imagine.Roald HoffmannAcknowledgementsI would like to thank several colleagues who accepted to read andre-read the manuscript during its preparation, and whose remarks andcomments were extremely useful to me: O. Eisenstein and C. Iung(Montpellier 2), J. Y. Saillard (Rennes 1), A. Strich (Strasbourg 1),I. Demachy (Paris Sud, Orsay), P. Le Floch and his group (D. Moores, M.Melaimi, N. Mezailles, M. Doux) at the Ecole Polytechnique (Palaiseau),R. Hoffmann (Cornell).
My thanks also go to J. Courtieu (Paris Sud,Orsay), thanks to whom I have been able to give a lecture course onorbital interactions to chemistry students since 1987, and to A. Lledos(Barcelona), who encouraged me to write this book at a time when Iwas hesitating. For various reasons, I am grateful to F. Mathey (Directorof the ‘Hétéroéléments et Coordination’ laboratory at the Ecole Polytechnique), L. Salem (founder of the laboratory ‘Chimie Théorique’ atOrsay), C. Pouchan (Pau), J.
C. Rayez (Bordeaux 1), J. L. Rivail (Nancy 1),A. Fuchs (Director of the ‘Laboratoire de Chimie Physique’ at Orsay),M. and P. Jean, for their help.This book also owes a large debt to the students who have followedmy lectures. In order to transmit knowledge and understanding, evenin an area which is completely familiar, it is necessary to clarify one’sideas so as to make a consistent and, if possible, attractive presentation.Students’ comments, remarks, and questions really help the teachers toachieve this goal.
When it comes to writing a manuscript, one realizesjust how useful the slow development and maturation of ideas has been.I am very honoured that Roald Hoffmann accepted to write thepreface, and the reader will discover during the chapters just how muchthe book owes to him.Ecole Polytechnique (Palaiseau)Université Paris Sud (Orsay)April 2004Introduction 1Chapter 1 Setting the scene 31.1.
Electron count in a complex: the covalent model 41.1.1. Ligand classification (L or X) 41.1.2. Electron count and the 18-electron rule 81.2. An alternative model: the ionic model 121.2.1. Lewis bases as ligands 121.2.2. Equivalence of the covalent andionic models: examples 141.3. Principles of orbital interactions 161.3.1. Interaction between two orbitals withthe same energy 161.3.2. Interaction between two orbitals withdifferent energies 171.3.3.
The role of symmetry 181.3.4. σ and π interactions 191.4. Metal orbitals 191.4.1. Description of the valence orbitals 201.4.2. Orbital energies 231.5. Ligand orbitals 241.5.1. A single ligand orbital: σ interactions 241.5.2. Several orbitals: σ and π interactions 261.6. Initial orbital approach to MLℓ complexes 301.6.1. Simplified interaction diagram 301.6.2. Strong-field and weak-field complexes 311.6.3. Electronic configuration and the18-electron rule 311.6.4. Analogy with the octet rule 32Exercises 33Chapter 2 Principal ligand fields: σ interactions 372.1.
Octahedral ML6 complexes 382.1.1. Initial analysis of the metal–ligand orbitalinteractions 382.1.2. Complete interaction diagram 412.1.3. Electronic structure 482.2. Square-planar ML4 complexes 512.2.1. Characterization of the d block 512.2.2. Electronic structure for 16-electron d8complexes 532.3. Square-based pyramidal ML5 complexes 53Contents2.3.1.
Characterization of the d block (metal in thebasal plane) 542.3.2. Characterization of the d block (metal out of thebasal plane) 562.3.3. Electronic structure and geometry 602.4. Tetrahedral ML4 complexes 622.4.1. Characterization of the d block 632.4.2. Electronic structure 662.4.3. ML4 complexes: square-planar ortetrahedral? 662.5. Trigonal-bipyramidal ML5 complexes 692.5.1.
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