Aspects of Homogeneous Catalysis: A Series of Advances

198 Pages·1974·4.311 MB·English

by  László Markó (auth.), Renato Ugo (eds.)

ASPECTS OF HOMOGENEOUS
CATALYSIS
Volume 2
ASPECTS
OF HOMOGENEOUS
CATALYSIS
A Series of Advances
EDITED BY
RENATO UGO
ISTITUTO or CHIMICA GENERALE ED INORGANICA
MILAN UNIVERSITY
VOLUME 2
D. REIDEL PUBLISHING COMPANY
I
DORDRECHT-HOLLAND BOSTON-U.S.A.
ISBN-13: 978-94-010-2287-3 e-ISBN-13: 978-94-010-2285-9
DOT: 10.1007/978-94-010-2285-9
Published by D. Reidel Publishing Company
P.O. Box 17, Dordrecht, Holland
Sold and distributed in the U.S.A., Canada and Mexico
by D. Reidel Publishing Company, Inc.
306 Dartmouth Street, Boston, Mass. 02116, U.S.A.
All Rights Reserved
Copyright © 1974 by D. Reidel Publishing Company, Dordrecht, Holland
SotIcover reprint of the hardcover I st edition 1974
No part of this book may be reproduced in any form, by print, photoprint, microfi'm,
or any other means, without written permission from the publisher
v
Editorial Board
L. Vaska
The Clarckson College of Technology N. Y. (U.S.A.)
E. W. Stern
Engelhard Industries (U.S.A.)
B. L. Shaw
The University of Leeds (U.K.)
A. Sacco
The University of Bari (Italy)
G. Pregaglia
Montecatini-Edison S.p.A. (Italy)
B. James
The University of British Columbia (Canada)
L. Sajus
Institut Fran9ais du Petrole (France)
H. C. Volger
Koninklijke/Shell Laboratorium (Holland)
L. Marko
University of Chemical Industries Academy of Science (Hungary)
M. Volpin
Institute of Organo-element Compounds Academy of Science
(USSR)
A. Misono
University of Tokyo (Japan)
J. Tsuji
Toyo Rayon Company (Japan)
J. Gardner
University of New South-Wales (Australia)
VII
Contents of Volume 2
Hydroformylation of Olefins with Carbonyl Derivates of the Noble Metals as Catalysts
Laszlb Markb
1. Introduction . . . . . . . . . . . . . . . . . . . . . 4
2. Comparison of the Activity of Group VIII Metals. . . . 5
3. Hydroformylation with Rhodium Complexes as Catalysts 8
4. Hydroformylation with Iridium Complexes as Catalysts . 41
5. Hydroformylation with Ruthenium and Osmium Complexes as Catalysts 42
6. Hydroformylation with Palladium and Platinum Catalysts . 44
7. Hydrogenation of Aldehydes with Carbonyl Derivatives of the Noble Me-
tals as Catalysts 45
8. Recent Results . 48
9. Conclusions 50
10. References. 51
Addition of hydrogen cyanide to mono-olefins catalyzed by transition metal complexes
E. S. Brown
1. Introduction and scope 57
2. Interaction of hydrogen cyanide with metal complexes . 58
3. Hydrocyanation of non-activated olefins 59
4. The proposed mechanisms of hydrocyanation 68
5. Hydrocyanation of activated olefins 71
VIII
6. Recent results 74
7. Conclusion 75
8. References. 76
Nickel Catalyzed Syntheses of Methyl-Substituted Cyclic Olefins, an Example of Step
wise Carbon-Carbon Bond Formation Promoted by a Transition Metal Complex
P. Heimbach
1. Introduction 81
2. Cope Rearrangement of 1,5-dienes . 84
3. Preparation of monomethyl derivatives by methylene insertion reaction
(MIR) . . . . . . . . . . . . . 92
4. Preparation of dimethyl derivatives by MIR . . . . . . . . 100
5. Identification of isomers using the combination gas chromatography/mass
spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . 109
6. Catalytic syntheses of mono and dimethyl substituted ring olefins 111
7. Mechanism of carbon-carbon bond formation promoted by low valent
nickel catalysts ........... ........ 130
8. Some general aspects of carbon-carbon and carbon-hydrogen bond for-
mation promoted by transition metals 140
9. References ............ 154
Dimerization of Acrylic Compounds
Masanobu Hidai and Akira Misono
1. Introduction. . . . . . . . . 159
2. Thermal and photo dimerization . 160
3. Dimerization by alkali metal amalgams and direct electrolysis 162
4. Phosphine-catalyzed dimerization. . . . . . 165
5. Dimerization by transition metal complexes. 171
6. Conclusion. 185
7. References. 185
ASPECTS OF HOMOGENEOUS
CATALYSIS
Volume 2
Chapter 1
Hydroformylation of Olefins
with Carbonyl Derivates
of the Nobles Metals as Catalysts
LAsZLO MARKO
Institute of Organic Chemistry, University of Chemical Industries, Veszprem, Hungary
1. Introduction 4
2. Comparison of the Activity of Group VIII Metals 5
3. Hydroformylation with Rhodium Complexes as Catalysts 8
3.1. SURVEY OF ApPLIED CATALYSTS AND CATALYST COMBINATIONS 8
3.1.1. Metallic Rhodium, Rhodium Carbonyls and Simple Rhodium Com-
pounds ........................... 8
3.1.2. Rhodium Catalysts Modified with Phosphines and Related Compounds 9
3.2. EFFECT OF HALOGEN ACCEPTORS AND NITROGEN COMPOUNDS 9
3.3. HYDROFORMYLATION OF OLEFINS . • . . • . . . . . . . . 12
3.3.1. Kinetics........................ 13
3.3.2. Isomerization of Olefins and Distribution of Isomeric Reaction Pro-
ducts ......... 15
3.3.3. Hydrogenation of Olefins . . . . 19
3.4. HYDROFORMYLATION OF DIOLEFINS 20
4
3.5. HYDROFORMYLATION OF SUBSTITUTED OLEFINS 20
3.6. HYDROFORMYLATION OF ACETYLENES 31
3.7. MECHANISM OF THE REACTION . . . 32
3.7.1. Hydroformylation with Unsubstituted Rhodium Carbonyls as Cata-
lysts . . . . . . . . . . . . . . . . . . . . . . . 32
3.7.2. Hydroformylation with RhH(CO)(PPh3)3 as Catalyst 33
3.7.3. Hydroformylation with Other Complexes 39
3.8. INDUSTRIAL ApPLICATIONS . . . . . . . 40
4. Hydroformylation with Iridium Complexes as Catalysts 41
5. Hydroformylation with Ruthenium and Osmium Complexes as Cata-
lysts . . . . . . . . . . . . . . . . . . . . . . . . 42
6. Hydroformylation with Palladium and Platinum Catalysts 44
7. Hydrogenation of Aldehydes with Carbonyl Derivatives of the Noble
Metals as Catalysts 45
8. Recent Results 48
9. Conclusions . 50
10. References. 51
1. INTRODUCTION
Cobalt carbonyl was regarded for a long time as the only catalyst suitable
for hydroformylation. This was ever the situation nearly a quarter of a century
after the discovery of the reaction by Roelen in 1938, although industry has
almost certainly devoted much effort to the search for other, more active or
more selective catalysts. Work was mainly directed towards iron and nickel,
the two neighbouring elements of cobalt in the periodic table, but in spite of
numerous efforts, no practical results could be achieved.
The development of new catalysts was hampered mainly by the prejudice
that the third neighbour of cobalt, rhodium is a "noble" metal. Noble metals
were regarded at that time by those working in this field of chemistry as che
mically unreactive and therefore not very interesting elements; the practical
use of which would be prohibited anyway by economic considerations. As
so often happens in science, it took considerable time to overcome this prejudice.
However, soon after it was recognized that the complexes of noble metals have
intriguing and useful catalytic properties, a breakthrough was achieved. This
occurred around 1965 and the past five years have brought a rapid advance in
the number of organic reactions catalyzed by noble metal complexes. One of
5
the most spectacular achievements in this respect was the development of hy
droformylation catalysts based on noble metals, especially the carbonyl complexes
of rhodium.
Rhodium and iridium carbonyls as catalysts for hydroformylation were
first mentioned in a patent of the Chemische Verwertungsgesellschaft Oberhaus en
m.b.H. [88] (inventor G. Schiller). This patent, which was disclosed in 1956
(and applied as early as 1952), correctly described the advantages of rhodium
(the use of lower temperatures and pressures and its higher activity relative to
cobalt), nevertheless it apparently remained unnoticed. It was evidently the
patent of the Esso Research and Engineering [52] (inventor V.L. Hughes),
disclosed in 1959, which received the necessary publicity and stimulated scien
tific research. The first publication in this field was the work of N. S. Imyanitov
and D. M. Rudkovskii [54] in 1963, which was then followed by a large number
of scientific contributions. The modification of the rhodium catalyst by using
phosphine complexes of rhodium or by adding phospines to the reaction mix
ture was first achieved by G. Wilkinson's school [75] and the researchers of the
Shell Oil [91] (L. H. Slaugh and R. D. Mullineaux) in 1965 and 1966, respecti
vely. This area has received the most attention in recent years, since the great
number of possible combinations offers a promising opportunity to find more
active and more selective catalysts.
Earlier reviews appeared in 1968 [47, 108] only partly covering the subject.
The present article covers the literature up to the end of 1971. An effort has been
made to cover patents as far as possible. This is seldom done in review articles,
partly because of the voluminous and at the same time inexact description of
experimental material and partly because of the lack of availability of the patent
data. However, experience often shows that patents may be good starting points
for basic research. To reduce the amount of data, only the examples and not
the claims were considered.
vm
2. COMPARISON OF THE ACTIVITY OF GROUP METALS
Before dealing separately with the noble metals as hydroformylation ca
talysts, their relative activities are compared in Tables 1-4. The data do not allow
any quantitative evaluation, but some qualitative comparisons can be made as
follows:
a) Rhodium is by far the most active metal for hydroformylation of mono
olefins, surpassing in this respect even the "classical" metal, cobalt.
b) Iridium and ruthenium carbonyls are already significantly less active
than cobalt, and OS3(CO)12 shows an even smaller activity.
c) The catalytic activity of platinum and palladium compounds in hydro
formylation is even less, although it must be mentioned that in the case of these
metals the experimental material is rather scanty (See Section 6.).