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4 Catalyst Stability; Degradation Routes, Losses and Recovery

4 Catalyst Stability; Degradation Routes, Losses and Recovery

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Catalysis by Metal Complexes

Volume 22



Editors:

B. R. James, The University of British Columbia, Vancouver, Canada

P. W. N. M. van Leeuwen, University of Amsterdam, The Netherlands

Advisory Board:

I. Horváth, Exxon Corporate Research Laboratory, Annandale, NJ, U.S.A.

S. D. Ittel, E. I. du Pont de Nemours Co., Inc., Wilmington, Del., U.S.A.

A. Nakamura, Osaka University, Osaka, Japan

W. H. Orme-Johnson, M.I.T, Cambridge, Mass., U.S.A.

R. L. Richards, John Innes Centre, Norwich, U.K.

A. Yamamoto, Waseda University, Tokyo, Japan



The titles published in this series are listed at the end of this volume.



RHODIUM CATALYZED

HYDROFORMYLATION

Edited by



PIET W.N.M. VAN LEEUWEN

Institute of Molecular Chemistry,

University of Amsterdam,

Amsterdam, The Netherlands

and



CARMEN CLAVER

Department de Quimica Física i Inorgánica,

Universitat Rovira i Virgili,

Tarragona, Spain



KLUWER ACADEMIC PUBLISHERS

NEW YORK / BOSTON / DORDRECHT / LONDON / MOSCOW



eBook ISBN:

Print ISBN:



0-306-46947-2

0-792-36551-8



©2002 Kluwer Academic Publishers

New York, Boston, Dordrecht, London, Moscow

All rights reserved

No part of this eBook may be reproduced or transmitted in any form or by any means, electronic,

mechanical, recording, or otherwise, without written consent from the Publisher

Created in the United States of America

Visit Kluwer Online at:

and Kluwer's eBookstore at:



http://www.kluweronline.com

http://www.ebooks.kluweronline.com



Preface

This book covers the developments in rhodium catalyzed

hydroformylation of the last decade, one of the most important reactions in

industry catalyzed by homogeneous catalysts. The work includes many of

the advances that have been made by academic and industrial researchers.

The field has undergone drastic changes, both in its industrial applications

and in our understanding. Clearly, the new advances pose new problems and

set new targets for future research.

In spite of the importance of the field, the last reviews covering a broad

area in hydroformylation are outdated (Falbe 1980, Pruett 1977) and it was

felt timely to bring together the recent developments. Only in the area of

aqueous biphasic hydroformylation there are several exhausting reviews

available. This is the first monograph on hydroformylation of this type and

for other processes there not many examples.

The aim of the book is to review the mainstream of the activities in the

field and not to present a complete coverage of the literature, not even the

recent literature. Several thousands of papers and patents deal with rhodiumcatalyzed hydroformylation and a complete review would be impossible. We

have chosen for a more didactic approach, in which we have tried to avoid

one-liners about publications. In the book one will find typical examples

about kinetics, applications in organic chemistry, industrial processes,

mechanistic understanding, etc. In the mainstream activities we have tried to

include industrial developments. We may have missed new catalyst systems

that are as yet small but may turn out to be of major importance later, but

that can hardly be avoided. New and important developments involving

other metals, such as cobalt, platinum, and palladium will also be absent.

While writing we had a broad audience in mind: chemists and engineers

in industry and academia with an interest in homogeneous catalysis, whose

backgrounds may be as varied as those of the present authors: inorganic,

organic, organometallic, catalytic, chemical engineering. It is hoped that

specialists in one area will read with interest the chapters on the

neighbouring expertise. The book is also meant for PhD-students and

advanced students interested in this area.

The combination of topics we have chosen is rather unique, connecting

studies on ligand effects, catalyst characterization, industrial requirements

regarding stability and separation, catalyst decomposition, and applications

xi



xii



Preface



in fine and bulk chemistry. The reader will notice the importance of one

discipline for the other. In many cases these relationships have already been

established, but for other cases the book might assist future developments.

The key roles that ligands may play in selectivity may be an eye-opener for

organic chemists and it will further enhance the large number of new

applications and reactions that are being discovered. The comments in

several chapters on catalyst preparation and feed purification may be useful

for scientists who are not specialized in homogeneous catalysis using

transition metal complexes.

Hydroformylation is also a model reaction system in homogeneous

catalysis as it contains so many aspects such as ligand effects (electronic,

steric, bite angle), in situ studies, complicated kinetics, and effects of

conditions and impurities. All this, combined with its practical value, makes

it an ideal topic in education.

The editors are very grateful to the authors for the good work they did

and the prompt responses. The writing took only a few months, as did the

production by the publisher. Writing the book has been rewarding, because

we learnt many things. Most of all perhaps, we obtained a clearer view on

what we still don’t fully understand.

Amsterdam, Tarragona

Piet van Leeuwen, Carmen Claver



TABLE OF CONTENTS



Preface



xi



1 Introduction to hydroformylation

Piet W. N. M. van Leeuwen

1.1 History of phosphorus ligand effects

1.2 Hydroformylation

1.3 Ligand parameters



1

1

6

8



15

2 Hydroformylation with unmodified rhodium catalysts

Raffaello Lazzaroni, Roberta Settambolo and Aldo Caiazzo

2.1 Introduction

15

2.2 Regioselectivity in the rhodium-catalyzed

hydroformylation of vinyl and vinylidenic substrates

16

2.2.1 Catalyst precursors

17

2.2.2 Influence of the alkene structure on the

regioselectivity

17

2.2.3 Influence of temperature

21

22

2.2.4 Influence of CO and H2 partial pressures

2.3 Mechanism of the hydroformylation of vinyl and

vinylidenic alkenes

22

2.3.1 Activation of the catalyst precursor

24

2.3.2 Behavior of the isomeric alkyl-metal intermediates

via deuterioformylation

24

2.3.3 In situ IR investigation of the formation and

reactivity of acylrhodium intermediates

28

2.4 Origin of the regioselectivity

29

2.4.1 Influence of the nature of the substrate

29

2.4.2 Influence of the reaction parameters

31

3 Rhodium phosphite catalysts

Paul C. J. Kamer, Joost N. H. Reek, and Piet W. N. M. van Leeuwen

3.1 Introduction

v



35

35



vi



Table of contents

3.2



3.3



3.4



3.5



Monophosphites

3.2.1 Catalysis

3.2.2 Mechanistic and kinetic studies

Diphosphites

3.3.1 Catalysis

3.3.2 Mechanistic and kinetic studies

Hydroformylation of internal alkenes

3.4.1 Hydroformylation of less reactive internal and

functionalized alkenes

3.4.2 Formation of linear aldehydes starting from

internal alkenes

Calixarene based phosphites



37

37

40

44

44

48

55

55

57

59



4 Phosphines as ligands

63

Piet W. N. M. van Leeuwen, Charles P. Casey, and Gregory T. Whiteker

4.1 Monophosphines as ligands

63

4.1.1 Introduction

63

4.1.2 The mechanism

64

4.1.3 Ligand effects

66

4.1.4 In situ studies

68

4.1.5 Kinetics

69

4.1.6 Regioselectivity

72

4.1.7 Conclusion

75

4.2 Diphosphines as ligands

76

4.2.1 Introduction

76

4.2.2 Ferrocene based diphosphine ligands

78

4.2.3 BISBI ligands and the natural bite angle

82

4.2.4 Xantphos ligands: tunable bite angles

87

4.2.5 The mechanism, regioselectivity, and

the bite angle. Concluding remarks

96

5 Asymmetric hydroformylation

107

Carmen Claver and Piet W.N.M. van Leeuwen

5.1 Introduction

107

5.2 Rhodium systems with chiral diphosphite ligands

109

109

5.2.1 C2 Symmetric chiral diphosphite ligands

5.2.2 Catalyst preparation and hydroformylation

111

5.2.3 Characterisation of [RhH(L)(CO)2] intermediates.

Solution structures of hydroformylation

catalysts

113

5.2.4 Structure versus stability and enantioselectivity 115



Table of contents



vii



Chiral cooperativity and effect of substituents in

diastereomeric diphosphite ligands

116

5.2.6 C1 Sugar backbone derivatives. Diphosphinite and

diphosphite ligands

121

124

Phosphine-phosphite rhodium catalysts

5.3.1 Introduction

124

5.3.2 Rhodium complexes with BINAPHOS and

related ligands

124

5.3.3 [RhH(CO) 2 (BINAPHOS)] complexes; models for

enantioselectivity

127

5.3.4 Separation studies for the BINAPHOS system 129

5.3.5 Chiral phosphine-phosphite ligands containing a

stereocenter in the backbone

129

Diphosphine rhodium catalysts

131

5.4.1 Introduction

131

131

5.4.2 C1 Diphosphines as chiral ligands

132

5.4.3 C2 Diphosphines as chiral ligands

5.4.4 The Rh/BDPP system. HPNMR and HPIR

studies under hydroformylation conditions

136

Mechanistic considerations

138

5.5.1 Regioselectivity

138

5.5.2 Enantioselectivity and conclusions

140



5.2.5



5.3



5.4



5.5



145

6 Hydroformylation in organic synthesis

Sergio Castillón and Elena Fernández

6.1 Introduction

145

6.2 Hydroformylation of unfunctionalized alkenes

146

6.3 Hydroformylation of functionalized alkenes

149

6.4 Substrate directed stereoselectivity

155

6.5 Control of the regio- and stereoselectivity by heteroatomdirected hydroformylation

160

6.6 Consecutive processes under hydroformylation

conditions

164

6.6.1 Hydroformylation-acetalization (intramolecular) 165

6.6.2 Hydroformylation-acetalization (intermolecular) 166

6.6.3 Hydroformylation-amination (intramolecular) 168

6.6.4 Hydroformylation-amination-reduction.

Hydroaminomethylation

172

6.6.5 Consecutive hydroformylation-aldol reaction 175

6.6.6 Consecutive hydroformylation-Wittig reaction 177

6.7 Alkyne hydroformylation

178

6.8 Concluding remarks

182



viii



Table of contents

7 Aqueous biphasic hydroformylation

Jürgen Herwig and Richard Fischer

7.1 Principles of biphasic reactions inwater

7.1.1 Why two-phase catalysis?

Scope and Limitations

7.1.2 Concepts for two-phase hydroformylation

7.2 Hydroformylation of propene and butene

7.2.1 Historic overview of two-phase

hydroformylation technology

7.2.2 Ligand developments

7.2.3 Kinetics and catalyst pre-formation

7.2.4 Process description

7.2.5 Status of the operated plants

7.2.6 Economics

7.3 Reaction of various alkenes

7.3.1 Ethylene to propanal: why not applied?

7.3.2 Long-chain alkenes

8 Process aspects of rhodium-catalyzed hydroformylation

Peter Arnoldy

8.1 Introduction

8.2 Economics

8.3 Catalyst selectivity and activity

8.3.1 Catalyst selectivity

8.3.2 Catalyst activity

8.4 Catalyst stability; degradation routes, losses and

recovery

8.4.1 Rhodium loss routes

8.4.2 Ligand loss routes

8.4.3 Catalyst recovery processes

8.5 Process concepts

8.5.1 Type I: Stripping reactor process/Rh

containment in reactor

8.5.2 Type II: Liquid recycle process/use of

distillative separation

8.5.3 Type III: Two-phase reaction/extraction process

8.5.4 Type IV: Extraction after one-phase reaction

8.6 Survey of commercialized processes and new

developments

8.6.1 Hydroformylation of butenes

8.6.2 Branched higher alkenes to mainly plasticizer

alcohols



189

189

189

190

191

191

191

193

196

197

198

199

199

200

203

203

204

206

206

207

208

208

209

210

211

212

213

2 15

216

220

220

223



Table of contents



8.6.3

8.6.4

8.6.5



Linear higher alkenes to mainly detergent

alcohols

1,4-Butanediol

Nylon monomers



ix



223

225

226



9 Catalyst preparation and decomposition

233

Piet W. N. M. van Leeuwen

9.1 Introduction

233

9.2 Catalyst preparation

233

9.3 Catalyst decomposition

235

9.3.1 Metal plating or cluster formation

235

9.3.2 Oxidation of phosphorus ligands

235

9.3.3 Phosphorus-carbon bond breaking in phosphines 237

9.3.4 Decomposition of phosphites

243

9.3.5 Formation of dormant sites

247

9.4 Concluding remarks

249

10 Novel developments in hydroformylation

253

Joost N. H. Reek, Paul C. J. Kamer, and Piet W. N. M. van Leeuwen

10.1 Introduction

253

10.2 New bimetallic catalysts

253

10.3 Novel developments in catalyst separation

256

10.3.1 Micellar catalysis

256

10.3.2 Supported aqueous phase catalysis (SAPC)

260

10.3.3 Hydroformylation in supercritical fluids

262

10.3.4 Fluorous Biphase catalysis

265

10.3.5 Dendrimer supported catalysts

267

10.3.6 Novel developments in polymer supported catalyst

269

10.4 Supramolecular catalysis

274

10.5 Conclusions

277

Index



281



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