THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS

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1 THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS

2 THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS Sixth Edition ROBERT H. CRABTREE Yale University, New Haven, Connecticut

3 Copyright 2014 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) , fax (978) , or on the web at Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) , fax (201) , or online at 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 specifically disclaim any implied warranties of merchantability or fitness 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 profit 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 or for technical support, please contact our Customer Care Department within the United States at (800) , outside the United States at (317) or fax (317) Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at Library of Congress Cataloging-in-Publication Data: Crabtree, Robert H., 1948 The organometallic chemistry of the transition metals / by Robert H. Crabtree. Sixth edition. pages cm Includes bibliographical references and index. ISBN (cloth) 1. Organometallic chemistry. 2. Organotransition metal compounds. I. Title. QD411.8.T73C dc Printed in the United States of America ISBN:

4 CONTENTS Preface List of Abbreviations xi xiii 1 Introduction Why Study Organometallic Chemistry?, Coordination Chemistry, Werner Complexes, The Trans Effect, Soft versus Hard Ligands, The Crystal Field, The Ligand Field, The sd n Model and Hypervalency, Back Bonding, Electroneutrality, Types of Ligand, 29 References, 37 Problems, 38 2 Making Sense of Organometallic Complexes The 18-Electron Rule, Limitations of the 18-Electron Rule, Electron Counting in Reactions, Oxidation State, 51 v

5 vi Contents 2.5 Coordination Number and Geometry, Effects of Complexation, Differences between Metals, 63 References, 66 Problems, 67 3 Alkyls and Hydrides Alkyls and Aryls, Other σ-bonded Ligands, Metal Hydrides, Sigma Complexes, Bond Strengths, 92 References, 95 Problems, 96 4 Carbonyls, Phosphines, and Substitution Metal Carbonyls, Phosphines, N-Heterocyclic Carbenes (NHCs), Dissociative Substitution, Associative Substitution, Redox Effects and Interchange Substitution, Photochemical Substitution, Counterions and Solvents in Substitution, 127 References, 129 Problems, Pi-Complexes Alkene and Alkyne Complexes, Allyls, Diene Complexes, Cyclopentadienyl Complexes, Arenes and Other Alicyclic Ligands, Isolobal Replacement and Metalacycles, Stability of Polyene and Polyenyl Complexes, 159 References, 160 Problems, Oxidative Addition and Reductive Elimination Introduction, Concerted Additions, 166

6 Contents vii 6.3 S N 2 Pathways, Radical Mechanisms, Ionic Mechanisms, Reductive Elimination, σ-bond Metathesis, Oxidative Coupling and Reductive Fragmentation, 180 References, 182 Problems, Insertion and Elimination Introduction, CO Insertion, Alkene Insertion, Outer Sphere Insertions, α, β, γ, and δ Elimination, 198 References, 201 Problems, Addition and Abstraction Introduction, Nucleophilic Addition to CO, Nucleophilic Addition to Polyenes and Polyenyls, Nucleophilic Abstraction in Hydrides, Alkyls, and Acyls, Electrophilic Addition and Abstraction, Single-Electron Transfer and Radical Reactions, 219 References, 221 Problems, Homogeneous Catalysis Catalytic Cycles, Alkene Isomerization, Hydrogenation, Alkene Hydroformylation, Alkene Hydrocyanation, Alkene Hydrosilylation and Hydroboration, Coupling Reactions, Organometallic Oxidation Catalysis, Surface, Supported, and Cooperative Catalysis, 251 References, 253 Problems, 256

7 viii Contents 10 Physical Methods Isolation, H NMR Spectroscopy, C NMR Spectroscopy, P NMR Spectroscopy, Dynamic NMR, Spin Saturation Transfer, T 1 and the Nuclear Overhauser Effect, IR Spectroscopy, Crystallography, Electrochemistry and EPR, Computation, Other Methods, 285 References, 287 Problems, M L Multiple Bonds Carbenes, Carbynes, Bridging Carbenes and Carbynes, N-Heterocyclic Carbenes, Multiple Bonds to Heteroatoms, 310 References, 313 Problems, Applications Alkene Metathesis, Dimerization, Oligomerization, and Polymerization of Alkenes, Activation of CO and CO 2, C H Activation, Green Chemistry, Energy Chemistry, 344 References, 347 Problems, Clusters, Nanoparticles, Materials, and Surfaces Cluster Structures, The Isolobal Analogy, Nanoparticles, 368

8 Contents ix 13.4 Organometallic Materials, 371 References, 379 Problems, Organic Applications Carbon Carbon Coupling, Metathesis, Cyclopropanation and C H Insertion, Hydrogenation, Carbonylation, Oxidation, C H Activation, Click Chemistry, 405 References, 406 Problems, Paramagnetic and High Oxidation-State Complexes Magnetism and Spin States, Polyalkyls and Polyhydrides, Cyclopentadienyl Complexes, f-block Complexes, 426 References, 433 Problems, Bioorganometallic Chemistry Introduction, Coenzyme B 12, Nitrogen Fixation, Nickel Enzymes, Biomedical and Biocatalytic Applications, 463 References, 465 Problems, 467 Appendix A: Useful Texts on Allied Topics 469 Appendix B: Major Reaction Types and Hints on Problem Solving 472 Solutions to Problems 475 Index 493

9 PREFACE This book is a study of the logic of organometallic chemistry as well as some of its leading applications. It should give starting scholars everything they need to set out on this field and develop their own approaches and ideas. I would again like to thank the many colleagues and readers who kindly pointed out errors in the fifth edition or otherwise contributed: Professors Pat Holland, Jack Faller, Yao Fu, Lin Pu, Samuel Johnson, Odile Eisenstein, Ann Valentine, Gary Brudvig, Alan Goldman, Ulrich Hintermair, and Nilay Hazari, as well as students Liam Sharninghausen, Nathan Schley, Jason Rowley, William Howard, Joshua Hummel, Meng Zhou, Jonathan Graeupner, Oana Luca, Alexandra Schatz, and Kari Young. I also thank the Department of Energy for funding our work in this area. New Haven, Connecticut August 2013 Robert H. Crabtree xi

10 LIST OF ABBREVIATIONS [ ] Encloses complex molecules or ions Vacant site or labile ligand Degrees Celsius 1, 2, 3... Primary, secondary, tertiary A Associative substitution (Section 4.5) acac Acetylacetonate AO Atomic orbital at. Pressure in atmospheres bipy 2,2 -Bipyridyl Bu Butyl ca. about cata Catalyst CIDNP Chemically induced dynamic nuclear polarization (Section 6.4) CN Coordination number cod 1,5-Cyclooctadiene coe Cyclooctene cot Cyclooctatetraene Cp, Cp* C 5 H 5, C 5 Me 5 Cy Cyclohexyl D Dissociative substitution mechanism (Section 4.4) D-C Dewar Chatt model of M(C=C) bonding involving weak back donation (Section 5.1) d n Electron configuration (Section 1.4) d σ, d π σ-acceptor and π-donor metal orbitals (see Section 1.4) diars Me 2 AsCH 2 CH 2 AsMe 2 dmf Dimethylformamide dmg Dimethyl glyoximate dmpe Me 2 PCH 2 CH 2 PMe 2 DMSO Dimethyl sulfoxide dpe or dppe Ph 2 PCH 2 CH 2 PPh 2 xiii

11 xiv List of Abbreviations e Electron, as in 18e rule E, E + Generalized electrophile such as H + e.e. Enantiomeric excess (Section 9.3) en H 2 NCH 2 CH 2 NH 2 EPR Electron paramagnetic resonance eq Equivalent or equatorial Et Ethyl eu Entropy units ev Electron volt (1 ev = 23 kcal/mol) fac facial (stereochemistry) Fp (C 5 H 5 )(CO) 2 Fe Hal Halogen HBpz 3 tris(pyrazolyl)borate HOMO Highest occupied molecular orbital hs high spin I Nuclear spin I Intermediate substitution mechanism IR Infrared L Generalized ligand, most often a 2e ligand (the L model for ligand binding is discussed in Section 2.1) L n M Metal fragment with n generalized ligands lin Linear lp Lone pair ls Low spin LUMO Lowest unoccupied molecular orbital m- Meta m r reduced mass MCP metalacyclopropane model of M(C=C) bonding involving strong back donation (Section 5.1) Me Methyl mer Meridional (stereochemistry) MO Molecular orbital N Group number of M (=number of valence e in the neutral atom) nbd Norbornadiene NHC N-heterocyclic carbene (Section 4.3) NMR Nuclear magnetic resonance (Sections ) NOE Nuclear Overhauser effect (Section 10.7) Np Neopentyl Nu, Nu Generalized nucleophile, such as H o- Ortho OA Oxidative addition OAc Acetate oct Octahedral (p. 5)

12 LIST OF ABBREVIATIONS xv OS Oxidation state (Section 2.4) oz. Ounce (28.35 g) p- Para Ph Phenyl pin Pinacolate py Pyridine RE reductive elimination rf radio frequency SET Single-electron transfer (Section 8.6) solv Solvent sq. pl. Square planar sq. py. Square pyramidal (Figure 1.5) T A structure with three of the ligands disposed as in the letter T T 1 Spin-lattice relaxation time tacn 1,4,7-triazacyclononane tacn* N, N,N -trimethyl-1,4,7-triazacyclononane tbe t-buch=ch 2 TBP or trig. bipy Trigonal bipyramidal (Figure 4.4) tet tetrahedral thf tetrahydrofuran TMEDA Me 2 NCH 2 CH 2 NMe 2 TMS trimethylsilyl Tp tris(pyrazolyl)borate (5.26) triphos MeC(CH 2 PPh 2 ) 3 Ts p-tolylso 2 TTP tricapped trigonal prism (Figure 2.1) VB Valence bond X Generalized 1e anionic ligand (see Section 2.1) Y A structure with three of the ligands disposed as in the letter Y + Partial positive charge δ Chemical shift (NMR) Δ Crystal field splitting (Section 1.6) Δ EN Electronegativity difference ΔG ΔH ΔS Free energy, enthalpy and entropy of activation needed to reach the transition state for a reaction η Hapticity in ligands with contiguous donor atoms (e.g., C 2 H 4. See Section 2.1) κ Hapticity in ligands with noncontiguous donor atoms (e.g., H 2 NCH 2 CH 2 NH 2 ; see Section 2.1) μ Descriptor for bridging with a superscript for the number of metals bridged, as in M 3 (μ 3 -CO) ν frequency

13 GROUP 1 Periodic Table of the Elements 1 H Li Be B C N O Na Mg Al Si P S K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po Fr Ra Ac Rf (261) 105 Db (262) 106 Sg (266) 107 Bh (262) 108 Hs (269) 109 Mt (266) 110 (273) 111 (272) 112 (294) Lanthanide series 58 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Actinide series 90 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md Note: Atomic masses shown here are the 1993 IUPAC values with a maxium of five significant figures (T. B. Coplen et al., Inorg. Chim. Acta 1994, 217, 217). An astcrisk indicates the mass of a commonly known radioisotope. Numbers in parentheses are the mass numbers of the corresponding longer-lived isotope F Cl Br I At Yb No He Ne Ar Kr Xe Rn Lu Lr xvi

THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS

THE ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS Second Edition ROBERT H. CRABTREE Yale University New Haven, Connecticut A Wiley-Interscience Publication JOHN WILEY & SONS New York / Chichester /