Table Of ContentADVANCES IN CATALYTIC ACTIVATION OF DIOXYGEN BY
METAL COMPLEXES
Catalysis by Metal Complexes
Volume 26
Editors:
Brian James, University of British Columbia, Vancouver, Canada
Piet W. N. M. van Leeuwen, University of Amsterdam, The Netherlands
Advisory Board:
Albert S.C. Chan, The Hong Kong Polytechnic University, Hong Kong
Robert Crabtee, Yale University, U.S.A.
David Cole-Hamilton, University of St Andrews, Scotland
István Horváth, Eotvos Lorand University, Hungary
Kyoko Nozaki, University of Tokyo, Japan
Robert Waymouth, Stanford University, U.S.A.
The titles published in this series are listed at the end of this volume.
ADVANCES IN CATALYTIC
ACTIVATION OF DIOXYGEN
BY METAL COMPLEXES
edited by
László I. Simándi
Chemical Research Center,
Hungarian Academy of Sciences, Budapest
KLUWER ACADEMIC PUBLISHERS
NEW YORK,BOSTON, DORDRECHT, LONDON, MOSCOW
eBookISBN: 0-306-47816-1
Print ISBN: 1-4020-1074-5
©2002 Kluwer Academic Publishers
NewYork, Boston, Dordrecht, London, Moscow
Print ©2003 Kluwer Academic Publishers
Dordrecht
All rights reserved
No part of this eBook maybe reproducedor transmitted inanyform or byanymeans,electronic,
mechanical, recording, or otherwise, without written consent from the Publisher
Created in the United States of America
Visit Kluwer Online at: http://kluweronline.com
and Kluwer's eBookstore at: http://ebooks.kluweronline.com
v
Preface
The subject of dioxygen activation and homogeneous catalytic oxidation
by metal complexes has been in the focus of attention over the last 20 years.
The widespread interest is illustrated by its recurring presence among the
sessions and subject areas of important international conferences on various
aspects of bioinorganic and coordination chemistry as well as catalysis. The
most prominent examples are ICCC, ICBIC, EUROBIC, ISHC, and of
course the ADHOC series of meetings focusing on the subject itself.
Similarly, the number of original and review papers devoted to various
aspects of dioxygen activation are on the rise.
This trend is due obviously to the relevance of catalytic oxidation to
biological processes such as dioxygen transport, and the action of oxygenase
and oxidase enzymes related to metabolism. The structural and functional
modeling of metalloenzymes, particularly of those containing iron and
copper, by means of low-molecular complexes of iron, copper, ruthenium,
cobalt, manganese, etc., have provided a wealth of indirect information
helping to understand how the active centers of metalloenzymes may
operate.
The knowledge gained from the study of metalloenzyme models is also
applicable in the design of transition metal complexes as catalytsts for
specific reactions. This approach has come to be known as biomimetic or
bioinspired catalysis and continues to be a fruitful and expanding area of
research.
This book is the sequel of the monograph Catalytic Activation of
Dioxygen by Metal Complexes by the editor of the present volume, published
by Kluwer Academic Publishers in 1992 as Volume 13 of the Series
Catalysis by Metal Complexes. Ten years later it is appropriate to cover the
developments in selected areas of the field, which has been the objective of
this edited volume in the same series.
It is my great pleasure to thank the authors of individual chapters for their
excellent contributions. The following prominent scientists have accepted
invitations to review major areas of dioxygen activation: Brian R.. James
(Catalytic oxidations using ruthenium porphyrins), Kenneth D. Karlin
(Copper-dioxygen complexes and their roles in biomimetic oxidation
reactions), Roger A. Sheldon (Catalytic oxidations of alcohols), Takuzo
Funabiki (Functional model oxygenations by nonheme iron complexes) and
Craig L. Hill (Catalysis for selective aerobic oxidation under ambient
conditions). A chapter on Catalytic oxidations using cobalt(II) complexes
has been contributed by myself.
vi
I am grateful to my wife Tatiana for her expert help at various stages of
the work and critical reading of Chapter 6. I thank Mary Egresi for her
assistance in the manuscript prepration.
László I. Simándi
Budapest
August2002
vii
Contents
Preface v
Contributors xiii
About the Editor xiv
Chapter 1
Catalytic oxidations using ruthenium porphyrins 1
Maria B. Ezhova and Brian R. James
Department of Chemistry, University of British Columbia, 2036 Main Mall,
Vancouver, BC, V6T1Z1, Canada
1. INTRODUCTION: OXYGENASE AND OXIDASE ACTIVITY 3
2. REACTIONS OF RUTHENIUM PORPHYRIN COMPLEXES
WITH AND OTHER OXIDANTS 12
3. OXIDATION OF ORGANIC SUBSTRATES 16
3.1 Oxidation of phosphines, phosphites, arsines and stibines 16
3.2 Oxidation of thioethers 19
3.3 Epoxidation of olefins 21
3.4 Oxidation of saturated hydrocarbons 40
3.5 Oxidative-dehydrogenation of phenols and other arenes 44
3.6 Oxidative-dehydrogenation of alcohols 47
3.7 Oxidative dehydrogenation of amines 51
4.CONCLUSIONS 61
5.ABBREVIATIONS 64
6.REFERENCES 66
Chapter 2
Copper-dioxygen complexes and their roles in biomimetic
oxidation reactions 79
Christiana Xin Zhang, Hong-Chang Liang, Kristi J. Humphreys and
Kenneth D. Karlin
Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA
1. INTRODUCTION 79
1.1 Practical Copper Oxidative Processes 80
1.2 Copper in Biology 80
1.2.1 Hemocyanin, Tyrosinase, and Catechol Oxidase 81
1.2.2 Amine Oxidases; Galactose Oxidase 84
viii
1.2.3Cytochrome c Oxidases 86
2. COPPER-DIOXYGEN ADDUCTS 86
2.1 Copper-Dioxygen Complex Generation; 1984-1999 87
2.2 Recent Further Advances in Copper-Dioxygen Complex
Generation 93
3. COPPER OXYGENASE CHEMISTRY 97
3.1 Aromatic Hydroxylation 97
3.2 Recent Tyrosinase Models 99
3.3 TPQ Biogenesis 101
3.4 Aliphatic Hydroxylation 103
4. COPPER OXIDASE MODELS; CATALYTIC ALCOHOL
OXIDATION 107
5. COPPER-PHENANTHROLINE DNA OXIDATION 111
6. REFERENCES 116
Chapter 3
Catalytic oxidations of alcohols 123
R.A. Sheldon and I.W.C.E. Arends
Biocatalysis and Organic Chemistry, Delft University of Technology, Julianalaan 136, 2628
BL Delft, The Netherlands
1. INTRODUCTION 123
2. MECHANISMS 124
3. RUTHENIUM-CATALYZED OXIDATIONS WITH 126
4. PALLADIUM-CATALYZED OXIDATIONS WITH 138
5. COPPER-CATALYZED OXIDATIONS WITH 144
6. OTHER METALS AS CATALYSTS FOR OXIDATION WITH 146
7. CATALYTIC OXIDATION OF ALCOHOLS WITH HYDROGEN
PEROXIDE AND ALKYL HYDROPEROXIDES 148
8. CONCLUDING REMARKS 151
9. REFERENCES 152
Chapter 4
Functional model oxygenations by nonheme iron
complexes 157
Takuzo Funabiki
Department of Molecular Engineering, Graduate School of Engineering,
Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
1. INTRODUCTION 158
ix
2. HEME AND NONHEME OXYGENASES 159
3. FUNCTIONAL MODEL STUDIES ON NONHEME IRON
DIOXYGENASES 161
3.1 Catechol Dioxygenases 161
3.1.1 Intradiol Cleavage Oxygenations 162
3.1.2 Extradiol Cleavage Oxygenations 170
3.1.3 Mechanisms of Oxygenations 173
3.2 Dioxygenases other than Catechol Dioxygenases 179
4. FUNCTIONAL MODEL SYSTEMS FOR NONHEME IRON
MONOOXYGENASES 181
4.1 Functional Model Oxygenations by Diiron Complexes 183
4.1.1 Monooxygenation by Diiron Complexes with Peroxides 183
4.1.2 Monooxygenation by Diiron Complexes with
Molecular Oxygen 187
4.2 Monooxygenation by Diiron Complexes 187
4.3 Functional Model Oxygenations by Iron Species in the
Polyoxometalate and Heterogeneous Matrix 189
4.3.1 Oxygenation by Iron Species in the Homogeneous
System 189
4.3.2 Oxygenation by Iron Species in the Heterogeneous
System 190
4.4 Functional Model Oxygenations by Mono-Iron Species 191
4.4.1 Oxygenation by Mono-Iron Complex/Activated Oxygen
System 191
4.4.2 Oxygenation by Mono-Iron System 198
4.4.3 Mono-Iron Oxygen Species 202
5. FROM FUNCTIONAL MODEL TO CATALYSIS 204
6. REFERENCES 207
Chapter 5
Catalysis for selective aerobic oxidation under ambient
conditions. Thioether sulfoxidation catalyzed by gold
complexes 227
Eric Boring, Yurii V. Geletii and Craig L. Hill
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA
1. INTRODUCTION 228
2. DISCOVERY OF CATALYTIC
OXIDATION SYSTEM 230
3. STOICHIOMETRIC Au(III) REDUCTION BY THIOETHERS 231
x
4. IN SITU CATALYST PREPARATION 232
5. REACTION STOICHIOMETRY 233
6. EMPIRICAL REACTION RATE LAW 235
7. RATE LIMITING STEP 237
8. PROPOSED REACTION MECHANISM 238
9. MECHANISMS RULED OUT 242
10.ORIGIN OF OXYGEN IN SULFOXIDE PRODUCT; ROLE
OF IN SULFOXIDATION 244
11.REOXIDATION OF Au(I) BY DIOXYGEN. CATALYST
PREPARATION FROM Au(I) COMPLEX 245
12.EFFECT OF LIGANDS ON REACTIVITY 247
13.PRODUCT INHIBITION (DMSO EFFECT) 249
14.CO-CATALYSIS BY TRANSITION METAL IONS 251
15.SOLVENT EFFECTS 252
16.HETEROGENEOUS SYSTEMS 255
17.EFFECT OF AMINO ACIDS 256
18.OXIDATION OF THIOETHERS OTHER THAN CEES 257
19.EXPERIMENTAL DETAILS 259
20.CONCLUSIONS 261
Chapter 6
Catalytic oxidations using cobalt(II) complexes 265
László I. Simándi
Chemical Research Center, Institute of Chemistry, Hungarian Academy of Sciences, H-1525
Budapest, P.O. Box 17, Hungary
1. INTRODUCTION 266
2. COBALT DIOXYGEN COMPLEXES 267
3. OXIDATIONS CATALYZED BY Co(salen) COMPLEXES 269
3.1 Oxidation of substituted phenols 269
3.1.1 2,6-di-tert-butylphenol 269
3.2 Oxidation of 3,5-di-tert-butylcatechol 270
3.3 Oxidation of lignin phenolics 270
3.4 Nitrogen monoxide 274
3.5 Oxidative dehydrogenation 275
3.6 Oxidation of quercetin 276
3.7 Mercaptoethanol 276
3.8 Alkenes and alcohols 276
3.9 Alkene epoxidation 278
3.10 Primary amines 280
4. OXIDATIONS CATALYZED BY COBALOXMES 280
