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  1. 1. THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS
  2. 2. THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS Fourth Edition ROBERT H. CRABTREE Yale University, New Haven, Connecticut A JOHN WILEY & SONS, INC., PUBLICATION
  3. 3. Copyright 2005 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. 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, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400, fax 978-646-8600, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specically disclaim any implied warranties of merchantability or tness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of prot or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. at 317-572-3993 or fax 317-572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print, however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data is available. ISBN 0-471-66256-9 Printed in the United States of America. 10 9 8 7 6 5 4 3 2 1
  4. 4. CONTENTSPreface ixList of Abbreviations xi1 Introduction 11.1 Werner Complexes, 21.2 The Trans Effect, 61.3 Soft Versus Hard Ligands, 81.4 The Crystal Field, 91.5 The Ligand Field, 141.6 Back Bonding, 151.7 Electroneutrality, 191.8 Types of Ligand, 212 General Properties of Organometallic Complexes 292.1 The 18-Electron Rule, 302.2 Limitations of the 18-Electron Rule, 352.3 Electron Counting in Reactions, 372.4 Oxidation State, 392.5 Coordination Number and Geometry, 412.6 Effects of Complexation, 452.7 Differences between Metals, 472.8 Outer-Sphere Coordination, 49v
  5. 5. vi CONTENTS 3 Metal Alkyls, Aryls, and Hydrides and Related-Bonded Ligands 533.1 Transition Metal Alkyls and Aryls, 533.2 Related -Bonded Ligands, 683.3 Metal Hydride Complexes, 723.4 Complexes, 753.5 Bond Strengths for Classical -Bonding Ligands, 794 Carbonyls, Phosphine Complexes, and Ligand SubstitutionReactions 874.1 Metal Complexes of CO, RNC, CS, and NO, 874.2 Phosphines and Related Ligands, 994.3 Dissociative Substitution, 1044.4 Associative Mechanism, 1094.5 Redox Effects, the I Mechanism, and Rearrangements inSubstitution, 1124.6 Photochemical Substitution, 1154.7 Steric and Solvent Effects in Substitution, 1185 Complexes of -Bound Ligands 1255.1 Alkene and Alkyne Complexes, 1255.2 Allyl Complexes, 1315.3 Diene Complexes, 1365.4 Cyclopentadienyl Complexes, 1405.5 Arenes and Other Alicyclic Ligands, 1485.6 Metalacycles and Isoelectronic and Isolobal Replacement, 1525.7 Stability of Polyene and Polyenyl Complexes, 1546 Oxidative Addition and Reductive Elimination 1596.1 Concerted Additions, 1626.2 SN2 Reactions, 1656.3 Radical Mechanisms, 1666.4 Ionic Mechanisms, 1696.5 Reductive Elimination, 1706.6 -Bond Metathesis, 1766.7 Oxidative Coupling and Reductive Cleavage, 1777 Insertion and Elimination 1837.1 Reactions Involving CO, 1857.2 Insertions Involving Alkenes, 1917.3 Other Insertions, 1977.4 , , , and Elimination, 199
  6. 6. CONTENTS vii8 Nucleophilic and Electrophilic Addition and Abstraction 2078.1 Nucleophilic Addition to CO, 2108.2 Nucleophilic Addition to Polyene and Polyenyl Ligands, 2138.3 Nucleophilic Abstraction in Hydrides, Alkyls, andAcyls, 2218.4 Electrophilic Addition, 2228.5 Electrophilic Abstraction of Alkyl Groups, 2268.6 Single-Electron Transfer Pathways, 2288.7 Reactions of Organic Free Radicalswith Metal Complexes, 2299 Homogeneous Catalysis 2359.1 Alkene Isomerization, 2399.2 Alkene Hydrogenation, 2419.3 Alkene Hydroformylation, 2549.4 Hydrocyanation of Butadiene, 2579.5 Alkene Hydrosilation and Hydroboration, 2619.6 Coupling Reactions, 2639.7 Surface and Supported Organometallic Catalysis, 26610 Physical Methods in Organometallic Chemistry 27510.1 Isolation, 27510.2 1 H NMR Spectroscopy, 27610.3 13 C NMR Spectroscopy, 28110.4 31 P NMR Spectroscopy, 28210.5 Dynamic NMR, 28410.6 Spin Saturation Transfer, 28810.7 T1 and the Nuclear Overhauser Effect, 29010.8 Isotopic Perturbation of Resonance, 29410.9 IR Spectroscopy, 29710.10 Crystallography, 30010.11 Other Methods, 30211 MetalLigand Multiple Bonds 30911.1 Carbenes, 30911.2 Carbynes, 32511.3 Bridging Carbenes and Carbynes, 32711.4 N-Heterocyclic Carbenes, 33011.5 Multiple Bonds to Heteroatoms, 33412 Applications of Organometallic Chemistry 34312.1 Alkene Metathesis, 34312.2 Dimerization, Oligomerization, and Polymerization ofAlkenes, 350
  7. 7. viii CONTENTS 12.3 Activation of CO and CO2, 36012.4 CH Activation, 36412.5 Organometallic Materials and Polymers, 37113 Clusters and the MetalMetal Bond 37913.1 Structures, 38013.2 The Isolobal Analogy, 39313.3 Synthesis, 39713.4 Reactions, 39913.5 Giant Clusters and Nanoparticles, 40713.6 Giant Molecules, 41114 Applications to Organic Synthesis 41714.1 Metal Alkyls Aryls, and Hydrides, 41814.2 Reduction, Oxidation, and Control of Stereochemistry, 42914.3 Protection and Deprotection, 43514.4 Reductive Elimination and Coupling Reactions, 43814.5 Insertion Reactions, 44314.6 Nucleophilic Attack on a Ligand, 44714.7 Heterocycles, 45414.8 More Complex Molecules, 45515 Paramagnetic, High-Oxidation-State, andHigh-Coordination-Number Complexes 46315.1 Magnetism and Spin States, 46415.2 Polyalkyls, 47115.3 Polyhydrides, 47615.4 Cyclopentadienyl Complexes, 47915.5 f -Block Complexes, 48116 Bioorganometallic Chemistry 49116.1 Introduction, 49216.2 Coenzyme B12, 49716.3 Nitrogen Fixation, 50316.4 Nickel Enzymes, 50916.5 Biomedical Applications, 517Useful Texts on Allied Topics 521Major Reaction Types 523Solutions to Problems 525Index 539
  8. 8. PREFACE I would like to thank the many colleagues who kindly pointed out corrections, or contributed in some other way to this editionJack Faller, Ged Parkin, Robin Tanke, Joshua Telser, Fabiola Barrios-Landeros, Carole Velleca, Li Zeng, Guoan Du, Ipe Mavunkal, Xingwei Li, Marcetta Darensbourg, Greg Peters, Karen Gold berg, Odile Eisenstein, Eric Clot and Bruno Chaudret. I also thank UC Berkeley for hospitality while I was revising the book. ROBERT H. CRABTREE New Haven, Connecticut January 2005 ix
  9. 9. LIST OF ABBREVIATIONS[] 1 , 2 , . . . A acac AO at. bipy Bu cata CIDNP CN cod coe cot Cp, Cp Cy + D d , d diars dpe or dppe Encloses complex molecules or ions Vacant site or labile ligand Primary, secondary, . . . Associative substitution (Section 4.4) Acetylacetone Atomic orbital Pressure in atmospheres 2,2 -Bipyridyl Butyl Catalyst Chemically induced dynamic nuclear polarization (Section 6.3) Coordination number 1,5-Cyclooctadiene Cyclooctene Cyclooctatetraene C5H5, C5Me5 Cyclohexyl Partial positive charge Chemical shift (NMR) Crystal eld splitting (Section 1.4) Dissociative substitution mechanism (Section 4.3) -Acceptor and -donor metal orbitals (see Section 1.4) Me2AsCH2CH2AsMe2 Ph2PCH2CH2PPh2 xi
  10. 10. xii LIST OF ABBREVIATIONS dmf Dimethylformamide dmg Dimethyl glyoximate dmpe Me2PCH2CH2PMe2 DMSO Dimethyl sulfoxide dn Electron conguration (Section 1.4) Shows hapticity in -bonding ligands (Section 2.1) E, E+ Generalized electrophile such as H+ e Electron, as in 18e rule e.e. Enantiomeric excess (Section 9.2) en H2NCH2CH2NH2 eq Equivalent Et Ethyl EPR Electron paramagnetic resonance eu Entropy units Fp (C5H5)(CO)2Fe fac Facial (stereochemistry) Hal Halogen HBpz3 Tris(pyrazolyl)borate HOMO Highest occupied molecular orbital I Nuclear spin I Intermediate substitution mechanism IPR Isotopic perturbation of resonance (Section 10.8) IR Infrared Shows hapticity in -bonding ligands (Section 2.1) L Generalized ligand, in particular a 2e ligand (L model for ligand binding is discussed in Section 2.1) LnM Generalized metal fragment with n ligands lin linear LUMO Lowest unoccupied molecular orbital Descriptor for bridging (Section 1.1) m- Meta Me Methyl mer Meridional (stereochemistry) mr Reduced mass MO Molecular orbital Frequency nbd Norbornadiene NMR Nuclear magnetic resonance (Sections 10.210.8) NOE Nuclear Overhauser effect (Section 10.7) Np Neopentyl Nu, Nu Generalized nucleophile, such as H o- Ortho OAc Acetate oct Octahedral (Table 2.5) ofcot Octauorocyclooctadiene
  11. 11. xiiiLIST OF ABBREVIATIONS OS Oxidation state (Section 2.4) p- Para Ph Phenyl py Pyridine RF Radio frequency SET Single electron transfer (Section 8.6) solv Solvent sq. py. Square pyramidal (Table 2.5) T1 Spin-lattice relaxation time tbe t-BuCH=CH2 thf Tetrahydrofuran triphos MeC(CH2PPh2)3 TBP or trig. bipy Trigonal bipyramidal (Table 2.5) TMEDA Me2NCH2CH2NMe2 TMS Trimethylsilyl Ts p-tolyl SO2 VB Valence bond X Generalized 1e anionic ligand (Se