Introduction to Metal π-Complex Chemistry

220 Pages·1970·13.71 MB·English

by  Minoru Tsutsui

INTRODUCTION TO METAL
1l'-COMPLEX CHEMISTRY
MONOGRAPHS IN INORGANIC CHEMISTRY
Editor: Eugene G. Rochow
Department of Chemistry, Harvard University
I. I. Vol'nov -
Peroxides, Superoxides, and Ozonides of Alkaline
Earth Metals - 1966
S. N. Borisov, M. G. Voronkov, and E. Va. Lukevits -
Organosilicon Heteropolymers and Heterocompounds -1970
M. Tsutsui, M. N. Levy, A. Nakamura, M. Ichikawa, and K. Mori -
Introduction to Metal TT-Complex Chemistry - 1970
INTRODUCTION TO METAL
IT-COMPLEX CHEMISTRY
MINORU TSUTSUI
Chemistry Department, Texas A&M University, College Station, Texas
MORRIS N. LEVY
Chemical and Solvent Distillers, Astoria, New York
AKIRA NAKAMURA
Department of Synthetic Chemistry, Osaka University, Toyonaka City,
Osaka, Japan
MITSUO ICHIKAWA
Research Laboratories, Japan Synthetic Rubber Company, Ikuta,
Mochiizaka, Kawasaki City, Japan
KAN MORI
Basic Research Division, Japan Synthetic Rubber Company, Ikuta,
Mochiizaka, Kawasaki City, Japan
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SPRINGER SCIENCE+BUSINESS MEDIA, LLC
ISBN 978-1-4757-5590-9 ISBN 978-1-4757-5588-6 (eBook)
DOI 10.10071978-1-4757-5588-6
Library of Congress Catalog Card Number 70-81164
© 1970 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1970
Softcover reprint of!he hardcover 1st edition 1970
AII rights reserved
No part of this publication may be reproduced in any form
without written permission from the publisher
Foreword
The Plenum Press series, Monographs in Inorganic Chemistry, is intended
to fill an obvious need for high-level surveys of recent research in that area,
particularly in matters which go beyond the traditional or classical bound
aries of the subject. The study of n-bonding of hydrocarbon groups (and their
derivatives) to metals is exactly that kind of subject, for it provides a new
way of understanding the behavior of metals (which constitute four-fifths
of all the chemical elements). In addition, n-bonding has expanded the
intriguing area of organometallic chemistry threefold, bringing in all the
transition metals, the lanthanides, and the actinides. So much has been
discovered and developed in the area of n-bonded "complexes" of the metals
that important new industrial processes based on such substances have
been developed.
A truly comprehensive review of all n-bonded compounds of the metals
would now result in an impossibly large and expensive volume, and would
require monthly revision. Instead, the present authors have wisely decided
to write a survey which outlines the general aspects of preparation, properties,
structure, reactions, and uses of such compounds-a survey which can serve
as a textbook, but which can also lead the more experienced practitioner
to the most advanced literature on the subject. They have clarified and
condensed the subject by means of good organization and a liberal use of
diagrams-features which will please the general reader. The authors are
to be commended for advancing the teaching and understanding of inorganic
chemistry, and we are happy to include this book in the series.
E. G. Rochow
v
Preface
In every generation achievements in science serve mankind. The progress
accomplished 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 structure of dicyclopentadienyliron (ferrocene), diben
zenechromium iodide, and olefin metal n-complexes, which provided an
introduction to a new type of chemical bond, the metaln-complex bond.
The stabilization and isolation of both cyclobutadiene and benzyne
derivatives were first achieved by their isolation as metaln-complexes because
of academic interest. However, industrial processes such as the Ziegler-Natta
olefin polymerization, the Wacker olefin oxidation of alcohols to aldehydes
and ketones, and the hydroformylation of olefins, among others, have pro
vided practical applications for achievements in metaln-complex chemistry.
Still to be determined are the exact role of metal n-complexes in many vital
biological functions and processes such as nitrogen fixation by plants.
Initial progress in the field of metal n-complexes followed the lines of
interest generated separately by organic and inorganic chemistry. However,
it is becoming increasingly clear that metal n-complex chemistry, bridging
both fields, flourishes independently.
As a consequence of the growth of this subject, both the senior and first
year graduate student as well as the working chemist will benefit from this
introduction to metal n-complex chemistry. Chapters 1 and 2 provide an
introduction to the nomenclature, classification, and preparation of metal
n-complexes. Current and historical views on the nature of the bond are
presented in Chapter 3 while the implications of the more significant physical
vii
viii Preface
properties, structure, and structure determination are discussed in Chapters 4
and 5. Chapter 6 presents a comprehensive study of the reactions of metal
n-complexes, although systematic mechanistic treatment awaits future
development. An area of continuing interest, catalysis involving metal
n-complexes, is discussed in Chapter 7.
Over a 5-year period, we surveyed and classified the literature in order to
formalize this new subject of chemistry. We have been fortunate to receive
the cooperation of the publishers, and we are grateful to the following
chemists who have reviewed the manuscript and offered constructive com
ments in spite of their busy schedules: M. Brintzinger, J. P. Collman, R.
Eisenberg, H. Gysling, M. Hancock, R. F. Heck, R. M. Hedges, D. Lorenz,
R. Pettit, M. Rausch, G. Redl, F. J. Smentowski, K. Suzuki, P. M. Treichel,
and R. Velapoldi.
We expect to revise the text, particularly with regard to the theoretical
and mechanistic treatment of the reactions of metal n-complexes, as new
developments occur in this area.
M. Tsutsui
M.N.Levy
A.Nakamura
M.Ichikawa
K.Mori
January 1969
Contents
Chapter 1. History, Classification, and Nomenclature. . . . . . . . . . . . . 1
1-1. History..................................... 1
1-2. Classification................................ 2
Olefin n-Complexes ........................ 2
n-Cyclopentadienyl complexes . . . . . . . . . . . . . . . 5
Arene n-Complexes ........................ 6
Additional Complexes . . . . . . . . . . . . . . . . . . . . . . 7
Heterocyclic Ring n-Complexes . . . . . . . . . . . . 7
Mixed n-Complexes . . . . . . . . . . . . . . . . . . . . . . 7
1-3. Nomenclature............................... 8
n-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Ligands in n-Complexes . . . . . . . . . . . . . . . . . . . . . 9
1-4. Exercises................................... 9
Chapter 2. Preparation of Metal n-Complexes . . . . . . . . . . . . . . . . . . . 13
2-1. Direct Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2-2. Redistribution Method ....................... 15
2-3. Metal Exchange ............................. 16
2-4. LigandExchange............................ 16
2-5. Addition Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2-6. Cyclization................................. 18
2-7. Rearrangements. . . . . . . . . . . . . . . . . . . . . . . . . . 20
(j-n
2-8. Substitution Methods. . . . . . . . . . . . . . . . . . . . . . . . . 21
2-9. Exercises................................... 26
2-10. Bibliography................................ 27
Chapter 3. Nature of the n-Complex Bond ...................... 29
3-1. Crystal Field Theory (CFT) . . . . . . . . . . . . . . . . . . . . 29
3-2. Valence Bond Theory (VBT) . . . . ..... . . . ... . . . . 30
ix
x Contents
3-3. Failure ofCFT and VBT ...................... 32
3-4. Molecular Orbital Theory (MOT). . . . . . . . . . . . . . . 33
3-5. Noble Gas Formalism ........................ 44
3-6. Exercises................................... 46
3-7. Bibliography................................ 48
Chapter 4. Spectroscopic and Magnetic Properties of Metal
n-Complexes .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4-1. Infrared Spectroscopy ........................ 49
Olefin n-Complexes ........................ 50
Acetylene n-Complexes . . . . . . . . . . . . . . . . . . . . . 52
Allyl n-Complexes (3 n-Systems) . . . . . . . . . . . . . . 53
Butadiene and Cyclobutadiene Complexes
(4n-Systems) ..... . . . . ...... . ... ... . ..... 54
n-Cyclopentadienyl Complexes (5 n-Systems) . . . 57
Arene n-Complexes ........................ 60
4-2. Nuclear Magnetic Resonance. . . . . . . . . . . . . . . . . . 61
Olefin Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 63
Ethylene and Mono-Olefin (2 n-System)
Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
n-Allyl (3 n-System) ........................ 67
Diolefins (Conjugated or Adjacent Double
Bonds; 4 n-System) . . . . . . . . . . . . . . . . . . . . . . . 71
n-Cyclopenatadienyl (5 n-System) . . . . . . . . . . . . 71
Arene (6 n-System) . . . . . . . . . . . . . . . . . . . . . . . . . 79
4-3. Mass Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4-4. Mossbauer Spectroscopy. . . . . . . . . . . . . . . . . . . . . . 81
4-5. Magnetochemistry........................... 84
4-6. Exercises................................... 87
4-7. Bibliography................................ 88
Chapter 5. Structure and Structure Determination. . . . . . . . . . . . . . . . 89
5-1. Isomerism in Metal n-Complexes .. . . . . . . . . . . . . . 90
Geometrical. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Structural. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Conformational ........................... 93
Optical... . .. . . . . . . . . . ..... . .... ... . . . ... . 94
5-2. Determination of Structure . . . . . . . . . . . . . . . . . . . . 95
Zeise's Salt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Ferrocene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Contents xi
Bis-Indenyliron(II)(Dibenzferrocene) . . . . . . . . . 100
n-Cyclopentadienyl-n-pyrrolyliron. . . . . . . . . . . . 101
Dibenzenechromium(O) . . . . . . . . . . . . . . . . . . . . . 103
Cyclo-octatetraene-Iron Tricarbonyl . . . . . . . . . . 104
5-3. Elucidation of Structure Without Conformation by
X-Ray Diffraction Data . .......... ....... ........ 107
Di-Diphenylchromium Iodides. . . . . . . . . . . . . . . 107
n-Cyclopentadienylnickel Azobenzene Complex. 109
5-4. Noveln-Complexes.......................... 110
Carborane-Metal Complexes. . . . . . . . . . . . . . . . 110
Hexamethyl Bicyclo [2.2.0] Hexa-2,5-Diene
Chromiumtetracarbonyl . . . . . . . . . . . . . . . . . . 115
5-5. Exercises................................... 115
5-6. Bibliography................................ 117
Chapter 6. ReactionsofMetaln-Complexes..................... 119
6-1. Reactions of Cyclopentadienyln-Complexes . . . . . . 119
Reactions of Ferrocene . . . . . . . . . . . . . . . . . . . . . . 120
Friedel-Crafts Acylation. . . . . . . . . . . . . . . . . . 121
Friedel-Crafts Alkylation . . . . . . . . . . . . . . . . . 122
Aminomethylation . . . . . . . . . . . . . . . . . . . . . . . 123
Sulfonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Formylation ............................ 123
Condensation. . . . . . . . .. . . . . . .. . . . . .. . . . . 123
Arylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Exchange Reactions. . . . . . . . . . . . . .. . . . . .. . 125
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
Reactions ofFerrocene Derivatives ........... 126
Reactions of Other Metallocenes. . . . . . . . . . . . . . 130
Addition Reactions. . . . . . . . . . . . . . . . . . . . . . . 130
Reduction Reactions ..................... 132
Oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Solvolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Reactions of Cyclopentadienyl Metal Carbonyls 134
6-2. Reactions of Olefin n-Complexes ............... 134
Addition Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 134
Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . 134
Protonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Addition of Hydrogen Chloride ............ 137