Organometallic Chemistry 0/ the Transition Elements

Organometallic Chemistry 0/ the Transition Elements

MODERN INORGANIC CHEMISTRY Series Editor: John P. Fackler, Jr. Texas A&M University CARBON-FUNCTlONAL ORGANOSILICON COMPOUNDS Edited by Vac1av Chvalovsky and Jon M. Bellama GAS PHASE INORGANIC CHEMISTRY Edited by David H. Russell HOMOGENEOUS CAT ALYSIS WITH METAL PHOSPHINE COMPLEXES Edited by Louis H. Pignolet THE JAHN-TELLER EFFECT AND VIBRONIC INTERACTIONS IN MODERN CHEMISTRY I. B. Bersuker METAL INTERACTIONS WITH BORON CLUSTERS Edited by Russell N. Grimes MÖSSBAUER SPECTROSCOPY APPLIED TO INORGANIC CHEMISTRY Volumes 1 and 2 Edited by Gary J. Long Volume 3 Edited by Gary J. Long and Fernande Grandjean ORGANOMETALLIC CHEMISTRY OF THE TRANSITION ELEMENTS Florian P. Pruchnik Translated from Polish by Stan A. Duraj A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher.

Organometallic Chmistry of the Transition Elements Florian P. Pruchnik Universily 01 Wroclaw Wroclaw, Poland Translated from Polish by Stan A. Dura} Cleveland Stale Universily Cleveland, Ohio Springer Science+Business Media, LLC

Library of Congress Cataloging in Publication Data Pruchnik, Florian P. Organometallic chemistry of the transition elements / Florian P. Pruchnik: translated from Polish by Stan A. Duraj. p. cm. -(Modern inorganic chemistry.) lncludes bibliographical references. ISBN 978-1-4899-2078-2 ISBN 978-1-4899-2076-8 (ebook) DOI 10.1007/978-1-4899-2076-8 I. Organometallic chemistry. 2. Transition metal compounds. I. Title. H. Series. QD4.11. -P78 1990 89-71115 547'.056-dc20 CIP 1990 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1990. Softcover reprint of the hardcover 1 st edition 1990 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

Preface Organometallic chemistry belongs to the most rapidly developing area of chemistry today. This is due to the fact that research dealing with the structure of compounds and chemical bonding has been greatly intensified in recent years. Additionally, organometallic compounds have been widely utilized in catalysis, organic synthesis, electronics, etc. This book is based on my lectures concerning basic organometallic chemistry for fourth and fifth year chemistry students and on my lectures concerning advanced organometallic chemistry and homogeneous catalysis for Ph.D. graduate students. Many recent developments in the area of organometallic chemistry as weil as homogeneous catalysis are presented. Essential research results dealing with a given class of organometallic compounds are discussed briefly. Results of physicochemical research methods of various organometallic compounds as weil as their synthesis, properties, structures, reactivities, and applications are discussed more thoroughly. The selection of tabulated data is arbitrary because, often, it has been impossible to avoid omissions. Nevertheless, these data can be very helpful in understanding properties of organometailic compounds and their reactivities. All physical data are given in SI units; the interatomic distances are given in pm units in figures and tables. I am indebted to Professor S. A. Duraj for translating and editing this book. His remarks, discussions, and suggestions are greatly appreciated. I also express gratitude to Virginia E. Duraj for editing and proofreading. I sincerely thank Professor A. Wojcicki for his comments, discussions, and editorial help. I also extend my thanks to Professors J. P. Fackler, Jr., F. A. Cotton, and R. A. Walton for their suggestions and remarks. My special thanks go to the chemistry faculty of Cleveland State University, especiaily to Professors A. H. Andrist and R. L. R. Towns for their support throughout the translation of the book. I also sincerely thank RicheIle P. Emery for her exceilent word processing skills in connection with the preparation of the English manuscript. The first Polish edition of this book appeared in 1984, and the second, expanded edition is now in press. v

vi Preface I should also like to acknowledge the comments and discussions of Professors S. Pasynkiewicz, A. Ratajczak, and W. Wojciechowski during the preparation of the Polish editions of this book. Finally, I sincerely thank my wife, Halina, for typewriting, proofreading, and for all her help during the writing and preparation of the book. F. Pruchnik

Contents Chapter I. Introduction to Organometallic Chemistry 1. Number of Va!ence E!ectrons. Characteristics of Ligands................... 1 2. The Main Group E!ements............................................ 7 3. The Transition Meta!s................................................ 11 4. E!ementary Reactions of Organometallic Compounds..................... 15 5. Nomenc1ature of Organometallic Compounds............................ 15 References... 20 Chapter 2. Metal Carbonyls 1. Preparation of Meta! Carbony!s........................................ 23 2. Bonding in Meta! Carbony!s........................................... 24 3. IR Spectra of Meta! Carbony!s......................................... 32 4. E!ectronic Spectra.................................................... 41 5. 13C NMR Spectra.................................................... 45 6. Photoe!ectron Spectroscopy........................................... 49 7. Mass Spectrometry................................................... 53 8. Properties of Meta! Carbony!s......................................... 55 a. Group 3 Meta! Carbony!s.......................................... 60 b. Group 4 Meta! Carbony!s.......................................... 63 c. Group 5 Meta! Carbony!s.......................................... 64 d. Group 6 Meta! Carbony!s.......................................... 69 e. Group 7 Meta! Carbony!s.......................................... 75 f. Group 8 Meta! Carbony!s.......................................... 79 g. Group 9 Meta! Carbony!s.......................................... 85 Cluster Compounds of Co, Rh, and Ir................................ 89 h. Group 10 Meta! Carbony!s......................................... 92 Meta! Carbony! Halides of Group 10 Meta!s........................... 94 i. Group 11 Meta! Carbony!s......................................... 95 9. Meta! Carbony! Hydrides............................................. 96 a. Bonding......................................................... 96 b. Methods of Identification........................................... 97 c. Preparation of Hydrido Comp!exes................................... 104 vii

viii Contents d. Acidic Properties of Metal Carbonyl Hydrides......................... 107 e. Ligand Field Strength and trans Effect of the Hydrido Ligand... " 107 f. Structures of Hydrido Complexes.................................... 107 g. Properties of Metal Carbonyl Hydrides............................... 108 10. Metal Carbonyls Containing Bridging CO Groups Bonded Through C and 0 110 11. Thiocarbonyl and Selenocarbonyl Complexes............................ 112 a. Structure, Bonding, and Spectroscopy................................ 112 b. Preparation of Thiocarbonyl and Selenocarbonyl Complexes............. 115 c. Reactions of Thiocarbonyl Complexes...,....... 116 12. Applications of Metal Carbonyl Complexes.............................. 119 13. Applications of Organometallic Compounds for Preparation of Metals, Oxides, Carbides, and Nitrides, and for Deposition of Metal Layers and Their Compounds... 119 14. Metal Carbonyl Complexes Possessing Column Structures................. 121 References... 122 Chapter 3. Metal-Metal Bonds and Clusters 1. Bonding and Structure................................................ 129 a. Theory of Ske1etal Electron Pairs.................................... 133 b. The Isolobal Analogy of Fragments.................................. 141 c. Topological Calculations of CVMO.................................. 147 d. Reactions between Clusters..., 149 e. Molecular Orbital Theory.......................................... 150 2. Clusters as Models of Metallic Lattices of Catalysts....................... 155 3. Interstitial (Encapsulated) Clusters..................................... 157 4. "Electron Poor" Transition Metal Clusters............................... 160 5. NMR Spectra of Clusters.............................................. 163 6. IR Spectra.......................................................... 165 7. The M - M Bond Energy in Clusters.................................... 166 8. Synthesis of Metal Clusters............................................ 166 9. Properties of Clusters................................................. 169 a. Group 4... " 169 b. Group 5.......................................................... 170 c. Group 6.......................................................... 170 d. Group 7... 171 e. Group 8.......................................................... 172 f. Group 9... " 174 g. Group 10......................................................... 175 h. Group 11......................................................... 177 10. Reactions of Clusters................................................. 179 a. Reactions Leading to Structural Changes in Clusters.................... 180 b. Migration of Ligands Within Clusters... " 183 c. Acid-Base Reactions... " 187 d. Ligand Substitution... " 190 e. Oxidative Addition................................................ 190 References... 193

Contents ix Chapter 4. Compounds Containing le Carbon-Donor Ligands 1. Bonding in Compounds with Metal-Carbon (J Bonds...................... 200 2. Stability of Compounds Containing 1e Ligands........................... 201 3. Structure of Compounds Containing Metal-Carbon (J Bonds............... 208 4. IR and Raman Spectra................................................ 212 5. NMR Spectra....................................................... 213 6. ESR Spectra......................................................... 215 7. Photoelectron Spectra................................................ 215 8. Magnetic Properties.................................................. 217 9. Electronic Spectra.................................................... 218 10. Preparation of Complexes Containing (J Bonded Carbon Ligands........... 219 a. Reactions of Transition Metal Compounds with Alkylating or Arylating Reagents......................................................... 219 b. Reactions Involving Oxidative Addition of Organic Halides.............. 220 c. Migration (Insertion) Reactions..................................... 222 d. Reactions of Anionic Complexes with Organic Halides.................. 224 e. Elimination of Neutral Group Connecting Carbon with Metal (Deinsertion)..................................................... 224 f. Preparation of Acetylide Complexes.................................. 225 g. Photochemical Synthesis............................................ 225 h. Electrochemical Synthesis........................................... 226 11. Properties of Complexes Containing Metal-Carbon (J Bonds..., 227 a. Complexes of Group 3 Metals..., 227 b. Complexes of Group 4 Metals....................................... 229 c. Complexes of Group 5 Metals....................................... 232 d. Complexes of Group 6 Metals....................................... 232 e. Complexes of Group 7 Metals....................................... 234 f. Complexes of Group 8 Metals....................................... 238 g. Complexes of Group 9 Metals....................................... 242 h. Complexes of Group 10 Metals...................................... 244 i. Complexes of Group 11 Metals...................................... 249 12. Reactions of Complexes Containing Metal-Carbon (J Bonds................ 253 a. The Breaking of the Metal-Carbon Bond............................. 253 b. Migration (Insertion) Reactions..................................... 255 c. Oxidative Addition Reactions....................................... 260 d. The (J-n; Rearrangement of Complexes Containing (J Metal-Carbon Bonds 261 13. Activation of Hydrocarbons........................................... 262 References... 269 Chapter 5. Carbene and Carbyne Complexes 1. Bonding............................................................ 277 2. Structures of Carbene and Carbyne Complexes........................... 281 3. IR Spectra.......................................................... 285 4. NMR Spectra....................................................... 285 5. Photoelectron Spectra................................................ 287 6. Electronic Spectra.................................................... 290 7. ESR and Magnetic Properties.......................................... 291

x Contents 8. Methods of Preparation of Carbene Complexes........................... 292 a. From Metal Carbonyls............................................. 292 b. Nucleophilic Addition to Isocyanide Ligands.......................... 292 c. Hydrogen Atom Abstraction from (J Bonded Carbon Ligands............ 294 d. Alkylation of Complexes with Some M - C (J Bonds.................... 295 e. Electrophilic Addition to Coordinated Ligands......................... 295 f. Reactions of Complexes with Mixtures of Acetylenes and Alcohols........ 295 g. Synthesis from Ionic Complexes..................................... 295 h. Oxidative Addition Reactions....................................... 296 1. Reactions of Complexes with Neutral Carbene Precursors............... 297 j. Nucleophilic Addition to Carbyne Complexes.......................... 298 k. Oxidation Reactions............................................... 298 1. Addition to Carbonyl Ligands....................................... 298 m. Synthesis of fl-methylene Complexes................................. 299 9. Methods of Preparation of Carbyne Complexes........................... 300 a. Removal of Alkoxy, Alkylthio, and Amino Groups from the Carbene Ligand.......... 300 b. Hydrogen Elimination from the Carbene Ligand....................... 300 c. Cleavage ofc=c Bonds in Acetylenes and C=N Bonds in Cyanides... 300 d. Reactions of Carbyne Complexes with Anionic Transition Metal Complexes..................................... 301 e. Spontaneous Carbene Ligand Rearrangement.......................... 301 f. Reactions of Acyl Complexes with Dibromotriphenyl Phosphorus(V)... " 301 g. Oxygen Abstraction from Acyl Ligands............................... 306 h. Protonation of Isocyanide Ligands................................... 306 i. Miscellaneous Methods of Synthesis of Carbyne Complexes.............. 306 10. Properties of Carbene and Carbyne Complexes........................... 307 11. Reactions of Carbene Complexes....................................... 308 a. Nucleophilic Substitution Reactions.................................. 308 b. Rearrangement Reactions Caused by Addition......................... 311 c. Hydrogen Substitution at ()(-C...................................... 312 d. Reduction of Carbene Complexes... " 312 e. Oxidation Reactions............................................... 313 f. Reactions with Electrophiles........................................ 314 g. Substitution Reactions ofnoncarbene Ligands......... 314 h. Release of Carbene Ligands... " 315 i. Migration Reactions............................................... 317 12. Reaction of Carbyne Complexes... " 317 a. Reactions with N ucleophiles... " 317 b. Reactions Leading to Bridging Carbyne Complexes..................... 318 c. Reactions of Carbyne Complexes with CO and CO 2..... 318 d. Removal of Carbyne Ligands........................................ 319 e. Exchange Reactions Involving Noncarbyne Ligands.................... 320 f. Reactions with Acids............................................... 320 g. Miscellaneous Reactions............................................ 320 13. Reactions of Complexes Containing Methylene Bridges.................... 320 14. Applications of Carbene and Carbyne Complexes......................... 322 References... 324

Contents xi Chapter 6. Compounds Containing Two-Electron n-ligands A. Olefin Complexes 1. Bonding and Structure................................................ 327 2. IR Spectra of Olefin Complexes........................................ 333 3. 1 H NMR Spectra.................................................... 335 4. 13C NMR Spectra.................................................... 337 5. Photoelectron Spectra................................................ 339 6. Electronic Spectra.................................................... 341 7. Stability of Olefin Complexes.......................................... 343 8. Methods of Synthesis of Olefin Compounds.............................. 347 a. Olefin Addition to the Transition Metal Salts.......................... 347 b. Addition of Olefins to Coordination Compounds of the Transition Metals 347 c. Substitution of Coordinated Ligands with Olefins...................... 347 d. Reduction in the Presence of Olefins.................................. 349 e. Preparation of Olefin Complexes from Hydrocarbon Ligands Coordinated to the Metal...................................................... 350 f. Exchange Reactions................................................ 350 g. Dehydration of Alcohols............................................ 351 h. Electrochemical Syntheses.......................................... 351 9. Properties of Transition Metal Olefin Complexes......................... 351 a. Group 4 Metal Complexes.......................................... 352 b. Group 5 Metal Complexes.......................................... 352 c. Group 6 Metal Complexes.......................................... 353 d. Group 7 Metal Complexes.......................................... 356 e. Group 8 Metal Complexes.......................................... 358 f. Group 9 Metal Complexes.......................................... 361 g. Group 10 Metal Complexes......................................... 368 h. Group 11 Metal Complexes......................................... 377 10. Complexes Containing Heteroolefins.................................... 379 11. Applications of n-olefin Complexes..................................... 381 a. Reactions of Olefin Complexes with Nucleophiles..., 381 b. Reactions of Olefin Complexes with Electrophiles...................... 384 c. Amination of Olefins............................................... 386 d. Olefin Exchange Reactions.......................................... 386 e. Substitution of Olefin Ligands....................................... 386 f. Transformation of Olefin Complexes into Vinyl Compounds............. 386 g. Hydrogen/Deuterium Exchange in Olefin Compounds.................. 387 h. Photochemical Reactions........................................... 388 B. Acetylene Complexes 1. Bonding and Structure................................................ 389 2. IR Spectra.......................................................... 392 3. NMR Spectra....................................................... 394 4. Methods of Preparation of Acetylene Complexes.......................... 396 a. Alkyne Addition to the Transition Metal Salts and Complexes........... 396 b. Ligand Substitution in Coordination Compounds...................... 397 5. Properties of Acetylene Complexes...................................... 398 6. Reactions of Acetylene Complexes...................................... 404 7. MetaIlacycIization Reactions........................................... 409

xii Contents 8. Complexes Containing R-C=Y and R-Y=C Ligands... 412 C. Allene Complexes 1. BondiIig and Structure................................................ 415 2. IR and NMR Spectra. Reactions of Allene Complexes..................... 417 References... 421 Chapter 7. Complexes Containing Three-Electron n-ligands 1. The Metal-Allyl Bond................................................ 427 2. IR Spectra of Allyl Complexes......................................... 431 3. NMR Spectra....................................................... 432 4. Electronic Spectra.................................................... 439 5. Structural Properties................................................. 441 6. Photoelectron Spectra................................................ 441 7. Methods of Preparation of n-allyl Complexes............................ 444 a. Reactions of Transition Metal Complexes with Allyl Compounds of Main Group Metals..................................................... 444 b. Reactions of Allyl Halides with Transition Metal Complexes in the Presence of Reducing Agents........................................ 444 c. Oxidative Addition of Allyl Halides.................................. 445 d. Reactions of Olefins with Metal Complexes............................ 445 e. Reactions of 1,3-Dienes with Metal Compounds........................ 446 f. Rearrangements of a-allyl Compounds to n-allyl Compounds........... 447 g. Synthesis of Metal Complexes Containing Chelated Allyl Ligands......... 447 h. Miscellaneous Methods............................................. 448 8. Properties of n-allyl Metal Compounds................................. 450 a. Complexes of Group 4 Metals....................................... 450 b. Complexes of Group 5 Metals....................................... 451 c. Complexes of Group 6 Metals....................................... 451 d. Complexes of Group 7 Metals....................................... 453 e. Complexes of Group 8 Metals....................................... 454 f. Complexes of Group 9 Metals....................................... 458 g. Complexes of Group 10 Metals...................................... 459 h. Complexes of Group 3 Metals....................................... 460 9. Cyclopropenyl Complexes............................................. 461 10. Heteroallyl Complexes................................................ 462 11. Reactions of Allyl Complexes.......................................... 463 a. Thermal Decomposition............................................ 463 b. Interactions with Nucleophilic Reagents; Oxidative Hydrolysis........... 464 c. Electrophilic Attack on Allyl Groups................................. 466 d. Formation of a-allyl Complexes..................................... 466 e. Reduction... 466 f. Reductive Elimination.............................................. 467 g. Migration (Insertion) Reactions of Ligands............................ 467 References... 468 Chapter 8. Compounds Containing Four-Electron n-ligands 1. The Bonding........................................................ 471 2. Structure of Compounds with 4e Ligands................................ 476

Contents xiii 3. NMR Spectra....................................................... 480 4. Photoelectron Spectra................................................ 485 5. IR Spectra.......................................................... 485 6. Methods of Preparation of l,3-diene Complexes.......................... 485 a. Reaction of Co ordination Compounds with Dienes..................... 485 b. Reactions Involving Nucleophilic Attack on Diene Complexes............ 488 7. Methods of Preparation of Cyclobutadiene Complexes..................... 489 8. Methods of Preparation of Trimethylenemethane Complexes............... 496 9. Reactions of l,3-diene Complexes...................................... 498 10. Reactions of Cyclobutadiene Complexes................................. 500 a. Thermal Decomposition............................................ 500 b. Ligand Substitution Reactions....................................... 500 c. Reactions Involving the Cyclobutadiene Ligand........................ 501 Nucleophilic Attack................................................ 501 Electrophilic Attack................................................ 502 d. Oxidation Reactions............................................... 502 e. Reduction Reactions............................................... 503 11. Reactions of Trimethylenemethane Complexes............................ 504 12. Properties of Diene Complexes......................................... 504 References... 505 Chapter 9. Compounds Containing Five-Electron n-ligands 1. The Metal-Cyclopentadienyl Bond..................................... 510 2. Structure of Cyclopentadienyl Complexes................................ 518 3. NMR Spectra....................................................... 520 4. IR Spectra.......................................................... 522 5. Magnetic Properties.................................................. 524 6. EPR Spectra........................................................ 525 7. Electronic Spectra.................................................... 525 8. Photoelectron Spectra................................................ 527 9. Thermochemistry of Cyclopentadienyl Complexes......................... 528 10. Mass Spectra........................................................ 529 11. Methods of Preparation of Cyclopentadienyl Complexes................... 530 a. Reactions Utilizing Cyclopentadiene in the Presence of Bases or Cyclopentadienyl Compounds of the Main Group Elements.............. 530 b. Syntheses Utilizing Fulvenes........................................ 531 c. Reactions of Transition Metal Compounds with Unsaturated Hydrocarbons... 532 d. Syntheses Utilizing Cyclopentadiene.................................. 533 e. Reactions of Dienes with Metal Vapors............................... 533 f. Preparation of Triple-Decker Cyclopentadienyl Complexes.............. 534 g. Preparation of Compounds Containing Bridging Cyclopentadienyl Ligands 536 h. Synthesis oftrinuclear M-P(O)(OR)2-Cyclopentadienyl Complexes... 536 i. Electrochemical Synthesis........................................... 537 j. Synthesis of Dienyl Complexes...................................... 537 12. Properties of Cyclopentadienyl Complexes............................... 538 a. Group 4 Metal Complexes.......................................... 538 b. Group 5 Metal Complexes.......................................... 541

xiv Contents c. Group 6 Metal Complexes.......................................... 543 d. Group 7 Metal Complexes.......................................... 545 e. Group 8 Metal Complexes.......................................... 545 f. Group 9 Metal Complexes.......................................... 548 g. Group 10 Metal Complexes......................................... 550 h. Group 11 Metal Complexes......................................... 551 i. Group 3 Metal Complexes Including Compounds of the Lanthanides and the Actinides...................................................... 551 13. Polynuc1ear and Cluster Cyclopentadienyl Complexes..................... 554 14. Pentadienyl Complexes............................................... 554 15. Pyrrole Complexes................................................... 555 16. Multidecker Complexes................................................ 556 17. Reactions of Cyclopentadienyl Compounds.............................. 557 a. Oxidation of Metallocenes and Electron Transfer Reactions.............. 557 b. Reduction of Cyclopentadienyl Complexes............................ 558 c. Protonation...................................................... 559 d. The M-cp Bond Rupture... 559 e. Metallation Reactions.............................................. 561 f. Aromatic Substitution Reactions..................................... 563 g. Preparation of Polymetallocenes..................................... 564 h. Ligand Substitution Reactions....................................... 564 i. Reactions with Substituents Containing Various Functional Groups....... 564 j. Activation of C - H Bonds.......................................... 565 k. Photochemistry of Cyclopentadienyl Complexes........................ 565 18. Application of Cyclopentadienyl Complexes.............................. 565 References... 569 Chapter 10. Complexes Containing Six-Electron n-ligands 1. The Bonding........................................................ 575 2. Electronic Spectra of Arene Complexes.................................. 578 3. Magnetic Properties.................................................. 578 4. IR Spectra.......................................................... 579 5. NMR Spectra....................................................... 579 6. Photoelectron Spectra................................................ 580 7. ESR Spectra.................. 582 8. Structure of Arene Complexes.......................................... 583 9. Thermochemistry of Arene Complexes................................... 584 10. Mass Spectra........................................................ 585 11. Properties of Arene Compounds........................................ 586 12. Asymmetric Arene Complexes.......................................... 588 13. Tripie Layer and Heteroarene Complexes................................ 588 14. Methods of Preparation of Arene Complexes............................. 590 a. Reactions of Transition Metal Compounds with Aluminum and Aluminum Chloride......................................................... 590 b. Reactions of Salts of Metals with Grignard Compounds................. 590 c. Cyclotrimerization of Acetylenes..................................... 591 d. Dehydrogenation of 1,3-Cyclohexadiene.............................. 592 e. Substitution of Ligands............................................. 592

Contents xv f. Reactions Involving Rearrangement of Ligands........................ 593 g. Condensation of Metal Vapors with Ligands........................... 594 h. Miscellaneous Reactions............................................ 594 15. Reactions of Arene Complexes......................................... 594 a. Redox Reactions.................................................. 594 b. Electrophilic Substitution Reactions.................................. 596 c. Nuc1eophilic Substitution and Addition Reactions...................... 596 d. Displacement of Ligands............................................ 598 16. Application of Arene Complexes........................................ 599 References... 600 Chapter 11. Complexes Containing Seven- and Eight-Electron n-ligands 1. Bonding, Structure, Spectroscopy, and Magnetic Properties................ 603 2. Properties of Cycloheptatrienyl and Cyc100ctatetraene Complexes... 607 3. Methods of Preparation of Cycloheptatrienyl and Cyc100ctatetraene Complexes... 609 4. Reactions of Cycloheptatrienyl and Cyclooctatetraene Complexes........... 611 a. Reactions with Nuc1eophiles........................................ 611 b. Oxidation and Reduction Reactions.................................. 613 c. Ligand Exchange Reactions in Complexes Containing CHT.............. 614 d. The M-CnHn Bond Breaking... 614 e. Metallation Reactions.............................................. 615 References... 616 Chapter 12. 1socyanide Complexes 1. Bonding and Structure................................................ 617 2. Electronic Spectra.................................................... 620 3. NMR Spectra....................................................... 621 4. IR Spectra.......................................................... 622 5. ESR Spectra and Magnetic Properties................................... 624 6. Ultraviolet and X-Ray Photoelectron Spectra............................ 624 7. Properties of Isocyanide Complexes..................................... 624 a. Group 3 Metal Complexes.......................................... 624 b. Group 4 Metal Complexes.......................................... 625 c. Group 5 Metal Complexes.......................................... 626 d. Group 6 Metal Complexes.......................................... 626 e. Group 7 Metal Complexes.......................................... 626 f. Group 8 Metal Complexes.......................................... 627 g. Group 9 Metal Complexes.......................................... 627 h. Group 10 Metal Complexes......................................... 628 i. Group 11 Metal Complexes......................................... 629 8. Methods of Synthesis of Isocyanide Complexes........................... 629 a. Preparations Involving Metal Cyanides and Cyanide Metal Complexes.... 629 b. Reactions ofisocyanides with Transition Metal Compounds............. 631 c. Oxidation and Reduction Reactions.................................. 632 9. Reactions of Isocyanide Complexes..................................... 632 a. Cleavage of the M - CNR Bond..................................... 632

xvi Contents b. Oxidation-Reduction Reactions..................................... 633 c. Oxidative Addition Reactions....................................... 634 d. Nucleophilic Addition.............................................. 634 e. Formation of Metal Carbyne Complexes.............................. 635 f. Insertion Reactions................................................ 636 g. Dimerization ofisocyanides......................................... 639 10. Applications ofisocyanide Complexes................................... 640 References... 641 Chapter 13. Application o/organometallic Compounds in Homogeneous Catalysis 1. Basic Principles...................................................... 647 a. Migration Reactions............................................... 652 b. Oxidative Coupling Reactions....................................... 654 c. Oxidative Addition Reactions....................................... 654 2. Hydrogenation...................................................... 655 a. Olefin Hydrogenation.............................................. 655 b. Hydrogenation of Aromatic Compounds.............................. 662 c. Asymmetrie Hydrogenation......................................... 662 d. Hydrogenation of the C = 0, C = N, and C == N Bonds................... 667 3. Isomerization of Olefins............................................... 670 a. Migration of the Double Bond...................................... 670 b. Cis-Trans Isomerization............................................ 673 4. Oligomerization and Polymerization of Olefins and Acetylenes.............. 674 a. Polymerization... 674 b. Oligomerization... 680 5. Carbonylation Reactions.............................................. 690 a. Hydroformylation Reactions........................................ 690 b. Carbonylation Reactions........................................... 694 c. The Stability of Phosphine-Containing Catalysts for Hydroformylation.... 701 6. Hydrocyanation..................................................... 702 7. Hydrosilation....................................................... 703 8. Metathesis... 704 a. Olefin Metathesis.................................................. 704 b. Mechanism of the Metathesis Reaction............................... 707 c. Metathesis of Functionalized Olefins................................. 713 d. Metathesis of Alkynes.............................................. 713 9. Disproportionation Reactions.......................................... 713 10. Reduction of Carbon Monoxide; the Fischer-Tropsch Synthesis............. 714 a. Mechanism ofthe Fischer-Tropsch Reaction.............. 716 11. Reactions of Carbon Dioxide.......................................... 725 12. Water-Gas Shift Reaction............ 729 13. Amination and Amoxidation Reactions............... 731 14. Heterogenized Homogeneous Catalysts.................................. 732 References... 736 Abbreviations... 745 Index... 749

Organometallic Chemistry 0/ the Transition Elements