ORGANOTRANSiTiON-METAl

CHEMisTRY

ORGANOTRANSiTiON-METAl

CHEMisTRY

Edited by

Yosl-tio Isl-ti i Department of Synthetic Chemistry Nagoya University Chikusa, Nagoya

and

Mi NORU TSUTSui Department of Chemistry Texas A&M University College Station, Texas

PLENUM PRESS • NEW YORK AND LONDON

Library of Congress Cataloging in Publication Data

Main entry under title:

Organotransition-metal chemistry.

Includes bibliographies and index. 1. Organometallic compounds-Congresses. 2. Transition metal compounds-Con-

gresses. I. Ishii, Yoshio, 1914- ed. II. Tsutsui, Minoru, 1918- ed. III. United States. National Science Foundation. IV. Nippon Gakujutsu Shinkokai. QD410.P76 547'.05 74-28165

ISBN-13: 978-14684-2144.e e-ISBN-13: 978-1-4684-2142-2 001: 10.1007/978-1-4684-2142-2

Proceedings of the first Japanese-American seminar on "Prospects in Organotransi­tion-Metal Chemistry," held at the University of Hawaii's East-West Center in Honolulu, May 1-3,1974 and jointly sponsored by the National Science Foundation

and the Japan Society for the Promotion of Science

© 1975 Plenum Press, New York

Softcover reprint of the hardcover 1 st edition 1975

A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N. Y. 10011

United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company, Ltd. 4a Lower John Street, London, W1 R 3PD, England

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

In every generation the achievements in science have served mankind. The progress accomplished by one generation stimulates the next generation to even greater achievements, which may take the form of increasing, crystallizing, or detailing existing theo­ries. Other forms, generally resulting from persistence and enlight­ened fortune, open new areas of investigation previously unimagined and have an impact that may be felt for many years.

An example of this latter form of achievement was the prepara­tion and elucidation of the structures of dicyclopentadienyliron (ferrocene, reported in 1951) dibenzenechromium iodide, triphenyl­chromium tristetrahydrofuranate, and numerous olefin-metal ~-com­plexes which provided an introduction to new types of chemical bonds­the sigma carbon-transition metal bond and the metal ~-complex bond.

Initial progress in the field of organotransition-metal chemis­try followed the lines of interest generated separately by organic and inorganic chemistry. However, it is becoming increasingly clear that organotransit10n-metal chemistry is not only bridging these two fields, but also crosslinking many other fields of science.

The stabilization and isolation of both cyclobutadiene and ben­zene derivatives of transition-metal organometallics were first a­chieved because of academic interest. However, industrial processes such as the Ziegler-Natta olefin polymerization, the Wacker oxidation of ethylene to aldehydes and ketones, and the hydroformylation of 0-lefins, among others, have provided practical applications for the achievements in organotransition-metal chemistry. Still to be deter­mined are the exact role of transition-metal organometallics in many metal biological functions and processes such as nitrogen fixation by nitrogenase and multifunctions of vitamin B12 and functions of or­ganomercury as a pollutant and catalytic functions in fuel cells.

During the past decade, a marked trend toward research on or­ganometallic chemistry by distinguished Japanese organic chemists has been observed. As a result, Japanese organotransition-metal chemists have demonstrated distinctive capabilities in discovering

v

vi PREFACE

new reactions and isolating unstable organotransition-metal com­pounds. On the other hand, many organotransition-metal chemists in the United States were originally inorganic chemists and have made outstanding contributions in specific areas of academic interest, such as the nature of bonding, structures, and mechanisms of reac­tions of organotransition-metal complexes.

While rapid progress in the field has been made during the past two decades, detailed mechanisms for only a few reactions of organo­transition-metals are known. It would seem that the mechanisms of more reactions could be better evaluated and understood by simulta­neously applying the characteristic approaches and research experi­ences that have been developed in both countries. For these reasons, it was most timely to hold a seminar on the following specific themes:

a. Factors influencing the stability of transition metal carbon bonds and mechanisms of the form and breaking of such bonds.

b. Mechanistic features of reactions involving unstable organotran­sition-metal complexes.

c. Application to catalytic processes, for example, carbonylation and related processes in which both countries have some scienti­fic and technological interest.

d. Application to environmental problems; notably the formation of toxic organometallic compounds such as methylmercury.

This bilateral meeting would benefit both countries in furtherance of their uniqueness of development in specialized areas, and in sti­mulating active interest in neglected and deficient areas in the field, which would be of the greatest benefit to science and society.

On May 1-3 the first Japanese-American seminar on "Prospects in Organotransition Metal Chemistry" was held at the University of Ha­waii's East-West Center, in Honolulu, jointly sponsored by the Na­tional Science Foundation and the Japanese Society for the Promotion of Science. The purpose of the seminar was to acquaint participants with the major trends and direction of research in each other's coun­try. Attendance was limited to l7 Japanese and 24 Americans in or­der to encourage informal discussion and exchange of ideas between the two nationalities.

This monograph includes 26 papers presented by the participants and nine papers invited by the editors. In order to provide spiri­tual and scientific feelings of the seminar, the outline of the ses­sions is described as follows:

There were six sessions of three to four hours length scheduled for the three days. No less than three full sessions were held on the first day in order to allow two subseQuent afternoons free for informal socializing on the beach.

PREFACE vii

Brief addresses by the Japanese and American organizers of the conference, Dr. Minoru Tsutsui and Dr. Yoshio Ishii, opened the first session, devoted to novel organometallic compounds. Two participants from U.C.L.A. dealt with compounds of unusual geometry: Dr. M. F. Hawthorne discussed his recent work in polyhedral expansion and con­traction of metallocarboranes, and Dr. H. D. Kaesz described unsat­urated ruthenium hydrido-carbonyl cluster complexes and their possi­ble application to catalysis. Presentations of work concerning com­pounds with novel ligands were represented by K, Itoh (Nagoya Univer­sity) on the bridging, bi-dentate behavior of benzoyl isocyanates and by Dr. R. B. King concerning complexes of polycyano olefins, specifically comparing the di-cyanovinylidene ligand with carbon monoxide. The only paper on the actinide metals was presented by Dr. Tobin Marks (Northwestern University) on tris(cyclopentadienyl) alkyl complexes.

The largest single topic of interest, covered from many view­points, was homogeneous catalysis. While the original controversy over the concerted vs. step-wise mechanism of various metal-catalyzed rearrangements has been largely resolved, four papers on this sub­ject were presented. First and foremost was Dr. R. Pettit's very thorough presentation on the concerted nature of silver ion catalyzed rearrangement of polycyclic hydrocarbons. Dr.'s Frank Mango (Shell Oil) and Robert Grubbs (Michigan State University) both discussed metallocycles as intermediates in these reactions, Dr. Mango in par­ticular questioned whether any reaction proceeding in this way should really be called "concerted". The Japanese contribution to this area was given by Dr. R. Noyori (Nagoya University) on nickel(O) catalyzed rearrangements involving highly strained a bonds.

Dr. J. Halpern, also active in homogeneous catalysis and a strong participant in the preceding discussion, presented a paper on a different aspect of catalysis - a detailed analysis of the me­chanism of catalysis by tris(triphenylphosphine) rhodium chloride. More specific applications of homogeneous catalysis were covered in papers by Dr. Jitsuo Kiji (Kyoto University) on diolefin polymeriza­tion catalyzed by Ni(O) complexes and acid, Dr. G. W. Parshall (Du­Pont) on activation (for exchange with deuterium gas) of aromatic C-H bonds, and Dr. Jiro Tsuji (Tokyo Institute of Technology) on addition reactions of butadiene catalyzed by palladium(II) complexes.

Two homogeneous catalytic reactions applicable to laboratory synthesis were presented: (1) the efficient catalytic coupling of Grignard reagents with aromatic halides by phosphine complexes of nickel (by Dr. M. Kumada, Kyoto University) and (2) the selective reduction of unsaturated ketones via rhodium catalyzed hydrosilyla­tion (by Dr. Iwao Ojima, Sagami Chemicals). The latter synthesis was also reported to have yielded products of up to 50% optical pur­ity from racemic substrate and chiral catalyst.

viii PREFACE

One most unusual and timely report was that of Northwestern Uni­versity's Dr. James Ibers, who had observed cationic rhodium-phos­phine complexes to homogeneously catalyze the conversion of CO and NO to CO2 and nitrogen.

In addition to the studies of catalytic reactions mentioned a­bove, the kinetics and mechanism of several other reactions were presented. Dr. J. Osborn (Harvard) analyzed the oxidative addition of alkyl halides to Pt(O), and concluded that such reactions general­ly occur via radical chain pathways. There were two contributors from Osaka University in this area; Dr. Akira Nakamura who examined the mechanism of a molybdenum dihydride complex with various unsat­urated compounds, and Dr. Toshio Tanaka, who had determined the ki­netics of TCNE addition to a cationic rhodium complex. Dr. G. Whitesides (MIT) managed to cover two topics in twenty minutes, the first on the decomposition mechanisms of metal alkyls and the second, some results on synthetically useful Li-Hg-C complexes of unknown structure. Further discussions of metal alkyl complexes were heard, one concerning nmr studies of nickel-alkyl phosphine complexes by Dr. Akio Yamamoto (Tokyo Institute of Technology), and a second a­bout decarboxylation of allyloxycarbonyl platinum(II) complexes by Dr. Hideo Kurosawa (Osaka University).

There were only two papers specifically on stereochemistry. Dr. Kazuo Saito (Tohoku University) concentrated on the asymmetric induction arising upon coordination of an olefin to chloro-L-proli­nato platinum (II), while Dr. J. Faller (Yale) lectured on the sub­stituents required to prevent palladium-allyl chiral centers from racemizing.

The last session was devoted to biological aspects of organo­metallic chemistry, dealing chiefly with the metalloporphyrin and -corrin systems. Dr. James Collman (Stanford) discussed a synthetic Iron(II) porphyrin with a hydrophobic "pocket" in which oxygen could be reversibly absorbed. Dr. Minoru Tsutsui of Texas A&M presented his work on some novel bimetallic rhenium porphyrins; Hisanbou Ogo­shi (KYoto University) also talked about noble-metal porphyrins, considering their similarity to vitamin B-12. For the final paper, Dr. John Wood (University of Illinois) presented his work on the me­chanism of mercury neurotoxicity, which arises from methylmercury ion catalyzed cleavage of a vinyl ether linkage found only in brain lipids.

The seminar was quite successful, and the organizers hope to re­peat it three years hence, although a meeting location has not been selected. In comparing the Japanese and American contriputions, the only general observation which might be made is that while the Japan­ese tended to collect more data, the Americans collected less, but analyzed it more thoroughly.

PREFACE ix

Heartfelt appreciation is extended to each of the authors and particularly to Jack Halpern, James P. Collman and Seinosuke Otsuka whose help in organizing this symposium. was invaluable. Also, we would like to express our gratitude to Mrs. Sally Hayes for an excellent job in the preparation and typing of this monograph.

Yoshio Ishii Minoru Tsutsui

Contents

SYNTHESIS OF ORGANOTRANSITION METALS

Metallocarboranes: Past, Present, and Future Frederick Hawthorne, Timm E. Paxson, K. P. Callahan, and Elvin L. Hoel

Novel Rhodium and Palladium Complexes with Benzoyl and Thiobenzoyl Isocyanates as Ligands • • • •

Kenji Itoh, Seiji Hasegawa, and Yoshio Ishii

Polycyanovinyl Transition Metal Derivatives • • R. Bruce King

A New Preparation of Organocopper(I)-Isonitrile Complexes and Their Reactions • • • • • • • • •

Takeo Saegusa and Yoshihiko Ito

An Unusual Behavior of ~-Vinyl Alcohol Complexes of Transition Metals • • • • • • • • • • • • • •

J. Francis, M. Ishaq, and M. Tsutsui

The Mode of Formation of Transition Metal to Carbon Bonds by Oxidative Addition • • • • • • • • • • • •

John A. Osborn

Organoactinides: Coordination Patterns and Chemical Reacti vi ty . . . . . . . . . . . . . . . . .

Tobin J. Marks

Recent Developments in Chemistry of Organolanthanides and Organoactinides • • • • • • • • • . • • • • • • •

Minoru Tsut sui, Carol Hyde, Alan Gebala, and Neal Ely

xi

1

25

37

57

81

93

xii

CATALYSIS BY ORGANOTRANSITION METALS

Mechanisms of Homogeneous Catalytic Hydrogenation and Related Processes ••••.•.•.••.

Jack Halpern

CONTENTS

109

Homogeneous Catalysis of Nickel Complexes. Oligomerization, Polymerization and Some Related Reactions of Diolefins. . . 119

Jitsuo Kiji and Junji Furukawa

Homogeneous Catalytic Activation of Hydrocarbons George W. Parshall

Metallocycles as Intermediates in Organotransition­Metal Reactions • . • • • • • • . . • • . • • • •

Robert H. Grubbs, Dale D. Carr, and Patrick L. Burk

Sequential Multistep Reactions Catalyzed by Polymer­Bound Homogeneous Ni, Rh, and Ru Catalysts •.•••

Charles U. Pittman, Jr. and Larry R. Smith

KINETIC AND MECHANISM OF REACTIONS AND CATALYSIS OF ORGANOTRANSITION METALS

127

135

143

Concerted Reactions of Organic Ligands on Transition Metals 157 Rowland Pettit

The Role of the Transition Metal in Catalyzing Pericyclic Reactions

Frank Mango

Reactions of Transition Metal Dihydrides. Mechanism of Reactions of Dihydrido-bis(~-cyclopentadienyl)­molybdenum with Various Unsaturated Compounds • . . •

Akira Nakamura and Sei Otsuka

Kinetics of the Addition of Tetracyanoethylene to Bis(Tertiary Phosphine)Bis(Isocyanide)Rhodium(I) Perchlorates " " " .. " .. " . . " .. . . . . .

Toshio Tanaka, Masa-aki Haga, Katsuhiko Kawakami

Catalytic Applications of Oxidative Addition of Alkyl Halides to Transition Metal Complexes

S. J. Lapporte and V. P. Kurkov

ORGANIC SYNTHESIS VIA ORGANOTRANSITION METALS

Phosphine-Nickel Complexes as Catalysts for Coupling Reaction of Grignard Reagents with Aromatic and Heteroaromatic Halides

Makoto Kumada

Cross­Vinylic,

181

191

199

211

CONTENTS

Mechanisms of Thermal Decomposition of Transition Metal Organometallic Compounds • • • • • • •

George M. Whitesides

Nickel(O) Catalyzed Reactions Involving Strained a-Bonds •• • . • • • • • • •

Ryoji Noyori

Some Synthetic Reactions by Means of Nickel

xiii

223

231

Carbonyl and Organic Halides . • • • • • • 243 Membo Ryang, Ilsong Rhee, Shinji Murai and Noboru Sonoda

Selective and Asymmetric Reductions of Carbonyl Compounds Using Hydrosilylation Catalyzed by Rhodium(I) Complexes .............• . . . . • • . 255

Iwao Ojima

Carbonylation Reactions of Organic Halides by Tetrakis(triphenylphosphine)nickel(O) and Palladium(O) Carbonyl Complexes under Mild Conditions . . . . 265

Masanobu Hidai, Yasuzo Uchida and Ikuei Ogata

The Palladium Catalyzed Reactions for Synthesis of Amines and Benzofurans . . . . • . . . . . . • .

S. -I. Murahashi, I. Moritani and T. Hosokawa

Chemistry of Alkylnickel Complexes. Preparation and Properties of Alkylnickels with Tertiary Phosphine Ligands . • . . . . . • . . • . • . .

Akio Yamamoto, Takakazu Yamamoto, Masakatsu Takamatsu, Toshio Saruyama and Yoshiyuki Nakamura

Studies of Hydrido Transition Metal Cluster Complexes Herbert Kaesz

A Facile Formation by Decarboxylation Complexes • • • •

Hideo Kurosawa

of n-Allylplatinum(II) Complexes of Allyloxycarbonylplatinum(II)

and Rokuro Okawara

Optical Inversion and SUbstitution of Coordinated Olefins in Optically Active trans(N)-Chloro-L­prolinato-olefin-platinum(II) Complexes in Organic Solvents .................. .

Kazuo Saito, Kazuo Konya, Junnosuke Fujita, Hiroaki Kido, and Yoshiro Terai

Conformational Equilibria and Stereospecific Synthesis . . . . . • •. ...... . .

Jack Faller

273

281

291

305

311

321

xiv CONTENTS

BIOLOGICAL AND RELATED ASPECTS

Synthetic Models for the Oxygen-Binding Hemoproteins . . . • 329 James P. Collman, Robert R. Gagne, and Christopher A. Reed

Organorhodium and Iridium Porphyrin Complexes a Model for Vitamin B12 . . . . . • •• .....• 345

Hisanobu Ogoshi, Jun-ichiro Setsune, Takashi Omura and Zen-ichi Yoshida

Unusual Metalloporphyrins • . . . . . . . . . . . . . 355 Minoru Tsutsui and Paul Hrung

The Catalyzed Reduction of Nitric Oxide by Carbon Monoxide using Soluble Rhodium Complexes . . .. ....• 369

Richard Eisenberg, Carol D. Meyer and Joseph Reed

Mechanisms for the Biosynthesis and Neurotoxicity of Methylmercury • • . • • . . . . • . • . • . . . . • . • . 377

John Wood

List of Authors •.•..•...•........•... 391

Subj ect Index . . . • . • . . . • . . . • • • • . • • . • . 395