ADVANCES IN SILICON SCIENCE

VOLUME 1

Series Editor:

JANIS MATISONSSchool of Chemistry, Physics and Earth Sciences, Flinders University,South Australia.

Advances in Silicon Science is a book series which presents reviews of the present and futuretrends in silicon science and will benefit those in chemistry, physics, biomedical engineering,and materials science. It is aimed at all scientists at universities and in industry who wish tokeep abreast of advances in the topics covered.

Series Editor

Professor Janis Matisons,Nanomaterials Group,

Chair of Nanotechnology,School of Chemistry, Physics and Earth Sciences,

Flinders University,GPO Box 2100,Adelaide 5001

SOUTH AUSTRALIA

Volume 1

Hydrosilylation: A Comprehensive Review on Recent Advances

Volume Editor

Professor Bogdan MarciniecDepartment of Organometallic Chemistry,

Adam Mickiewicz University,Poznan,

POLAND.

For other titles published in this series, go to http://www.springer.com/series/7926

Hydrosilylation

Bogdan MarciniecEditor

Hydrosilylation

A Comprehensive Review on RecentAdvances

Contributing authors

Bogdan Marciniec, Hieronim Maciejewski, CezaryPietraszuk, Piotr Pawluc

Adam Mickiewicz University, Poland

123

Editor

Prof. Dr. Bogdan MarciniecA. Mickiewicz UniversityFaculty of ChemistryGrunwaldzka 660-780 PoznanPolandBogdan.Marciniec@amu.edu.pl

Contributing authorsBogdan Marciniec Bogdan.Marciniec@amu.edu.plHieronim Maciejewski maciejm@amu.edu.plCezary Pietraszuk pietrasz@amu.edu.plPiotr Pawluc piotrpaw@amu.edu.pl

Department of Organometallic Chemistry, Faculty of Chemistry, Adam MickiewiczUniversity, Poznan, Poland

ISBN: 978-1-4020-8171-2 e-ISBN: 978-1-4020-8172-9

DOI 10.1007/978-1-4020-8172-9

Library of Congress Control Number: 2008933939

c© Springer Science+Business Media B.V. 2009No part of this work may be reproduced, stored in a retrieval system, or transmittedin any form or by any means, electronic, mechanical, photocopying, microfilming, recordingor otherwise, without written permission from the Publisher, with the exceptionof any material supplied specifically for the purpose of being enteredand executed on a computer system, for exclusive use by the purchaser of the work.

Printed on acid-free paper

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Preface

Since the discovered of the catalyzed hydrosilylation of olefins by chloroplatinicacid in the mid 1950’s, the original reaction and its numerous off-spring have showna steady and continuous growth over the subsequent half-century. A number of ex-cellent specialized reviews have appeared periodically since the original report, butthe appearance of Professor Marciniec’s “Comprehensive Handbook on Hydrosi-lylation” in 1992 was a landmark in the discipline. By that time the scope of thehydrosilylation reaction had been extended to include a wide range of additionalunsaturated substrates. Its utiliarian scope had expanded far beyond its early spe-cialized application to the technology of silicones, particularly into general organicsynthesis and specialty materials chemistry. Hydrosilation mechanisms, subjects oflively debate for many years, were beginning to be firmly establised with the aidof improved experimental and theoretical tools. “Comprehensive Handbook on Hy-drosilylation” provided the most thorough coverage of all aspects of the subject atthe time of its publication and quickly became an obligatory volume for librariesand a highly respected resident of any synthetic chemist’s bookshelf. One reviewerof the subject’s assessment was that Marciniec’s Handbook “is considered by manyas the “Bible” on hydrosilylation”.

Time never stands still in the world of useful and interesting science, and thisis certainly true of the world of hydrosilylation chemistry. Novel uses of hydrosi-lylation for the modification of materials appear almost daily. Functionalization ofpolymers and surfaces, stereo-, regio- and enantioselective synthesis of new andold molecules, construction of dendrimers and other novel molecular architectures,are but few of the many areas where this chemistry has had an important influence.Even in the area of mechanistic studies the subtle variations within the several “clas-sical” reaction paths continue to be enriched by both experimental and theoreticalapproaches. Quite recently, a completely new and unprecedented mechanism forthe hydrosilylation of 1-alkenes was reported (see:Glaser-Tilley mechanism in thepresent volume). All this is to say that it is time for a new, comprehensive overviewof the subject. The present volume, “HYDROSILYLATION: A Comprehensive Re-view of Recent Advances” fulfills this need with the same systematic thoroughnessthat characterized “Comprehensive Handbook on Hydrosilylation”. This extensivelyresearched and well organized volume brings every aspect of the subject up to date.

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viii Preface

I have no doubt it will quickly acquire a reputation as the “New Testament” com-panion to the earlier volume.

McGill University, Montreal, QC, Canada John F. HarrodAugust, 2008

Biographical Note

Prof. Bogdan Marciniec

Photograph of Prof. Bogdan Marciniec reproduced with permission from KRZYSZTOF KOŁECKI.

Copyright KRZYSZTOF KOŁECKI.

Professor Bogdan Marciniec, received M.Sc. (1963), Ph.D. (1970) and D.Sc. (1975)from the Adam Mickiewicz University, Poznan, Poland. Member of the PolishAcademy of Sciences (1994). Head of the Department of Organometallic Chem-istry (1987), President of the Adam Mickiewicz University (1988/1990), Director ofCenter of Excellence – Center of Silicon Chemistry (2000). He was a postdoctoralassociate with Prof. R.C. Schowen, Kansas University (1970/1971).

His research activity is focused on the organosilicon chemistry and catalysisby organometallic compounds. Synthesis and catalytic reactions of the substitutedsilanes and (poly)siloxanes such as hydrosilylation of C=C and C≡C bonds, cross-metathesis and silylative coupling of olefins with vinylsilicon compounds, polycon-densation, ADMET polymerisation and ring-closure metathesis of silicon contain-ing dienes are of particular interest.

ix

x Biographical Note

Activation of =C-H and ≡C-H bonds by M-Si, (silicometallics) as well as byM-B, M-Ge, M-Sn (general inorganometallics) and M-H complexes (where M =Ru, Rh, Ir, Cro, Fe) has been also his interest to lead towards new organometallicreagents for organic and asymmetric synthesis as well as precursors of new ma-terials (including polymers) of special physico-chemical or optoelectronic proper-ties. He is an author and co-author of 300 publications and 22 book chapters e.g.Handbook of Metathesis (Wiley-VCH, 2003), Encyclopedia of Catalysis, (J.Wiley& Sons, Inc. N.Y., 2003), Applied Homogeneous Catalysis with OrganometallicCompounds (Wiley-VCH, 2002) as well as editor and co-author 12 books inter alia“Comprehensive Handbook on Hydrosilylation” (Pergamon Press, 1993), “Progressin Organosilicon Chemistry” (Gordon & Breach Publ., 1995). Professor Bog-dan Marciniec was awarded of the Prime Ministry Award (2001) and J.SniadeckiMedal of the Polish Chemical Society (2003) for the outstanding achievementsin chemistry. He is or was a member of Editorial Board of such journals asOrganometallics, Applied Organometallic Chemistry, Clean Products & Processesand Encyclopedia Britannica (Polish Edition) as well as a member of AdvisoryBoards of International Symposia – International Symposium on OrganosiliconChemistry (since 1993), International Symposium on Olefin Metathesis and Poly-merisation (1993), European Silicon Days (2000) and International Symposium onHomogeneous catalysis (2008). He was a Chairman of the Xth International Sympo-sium on Organosilicon Chemistry – Poznan (1995), 16th International Symposiumon Olefin Metathesis – Poznan (2005) and will be the chairman of the 17th Interna-tional Symposium on Homogeneous Catalysis (2010).

Abbreviations

acac acetylacetonateACCN 1,1′-azobis(cyclohexanecarbonitrile)AIBN azobisisobutyronitrilet-Am tert-AmylAr-Bian 1,2-bis (arylimino)acenaphthene ligandsBINAP 2,2′-bis(diphenylphosphino)-1, 1′-binaphtylBMin 1-butyl-3-methylimidazolinumBn benzylBOC tert-butoxycarbonylbq benzoquinonecod 1,5-cyclooctadienecoe cycloocteneCp cyclopentadienylCp∗ pentamethylcyclopentadienylm-CPBA meta-chloroperoxybenzoic acidCPU Central Processing UnitCy cyclohexyldba dibenzylideneacetoneDCE 1,2-dichloroethaneDCM dichloromethanedcpe 1,2-bis(dicyclohexylphosphino)ethaneDFT Density Functional TheoryDIBAH diisobutylaluminum hydridedippe 1,2-bis(diisopropylphosphino)ethaneDMAP 4-dimethylaminopyridineDMF dimethylformamideDMSO dimethyl sulphoxideDPE diphenylethylenedppm bis(diphenylphosphino)methaneDppp 1,3-bis(diphenylphosphino)propaneDVB divinylbenzenedvds 1,3-divinyltetramethyldisiloxane

xi

xii Abbreviations

EDTA ethylenediaminetetraacetateee enantiomeric excessEXAFS Extended X-ray Absorption Fine StructureFc ferrocenylGPC Gel Permeation Chromatographyhfac hexafluoroacetylacetonateHMG 3-hydroxy-3-methyl glutaric acidInd indenylLIM Liquid injection moldingLED Light emitting diodesMen menthylMes mesitylMes∗ 2, 4, 6-tri-tert-butylphenylMn number average molecular weightMOM methoxymethylMTPA α-methoxy-α-(trifluoromethyl)phenylacetic acidMw weight average molecular weightMW microwave irradiationnbd norbornadienenbe norborneneNBS N -bromosuccinimideNHC N -heterocyclic carbeneOTf triflate (-OSO2CF3)OTs tosylatePDI Polydispersity Indexphen phenanthrolinepic 2-pyridinecarboxylatePiv pivaloylPMBn p-methoxybenzylPMHS polymetylhydrosiloxanePy pyridylSDS sodium dodecyl sulphateTBAB tetrabutylammonium bromideTBAF tetrabutylammonium fluorideTBDMS tert-butyldimethylsilylTBDPS tert-butyldiphenylsilylTFA trifluoroacetic acidTHF tetrahydrofuranTHP tetrahydro-2H-pyran-2-ylTIPS triisopropylsilylTM transition metalTMDS tetramethyldisiloxaneTMEDA tetramethylethylenediamineTMS trimethylsilyl

Abbreviations xiii

TOF turnover frequencyTON turnover numberTPFPB tetrakispentafluorophenyl borateTPS triphenylsilylTriMIM tris(imidazolyl)

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix

Part I Hydrosilylation of Carbon----Carbon Multiple Bonds in Synthesisof Molecular Organosilicon Compounds

1 Hydrosilylation of Alkenes and Their Derivatives . . . . . . . . . . . . . . . . . . 31.1 Late Transition Metal Complexes as Catalysts . . . . . . . . . . . . . . . . . . 4

1.1.1 Mechanism and Side Reactions of Transition MetalComplex Catalysed Hydrosilylation . . . . . . . . . . . . . . . . . . 4

1.1.2 Platinum Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81.1.3 Palladium and Nickel Complexes . . . . . . . . . . . . . . . . . . . . . 121.1.4 Cobalt Triad Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171.1.5 Iron Triad Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

1.2 Early Transition Metal, Lanthanide and Actinide Complexesas Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

1.3 Photo- and Peroxide-Initiated Catalysis by Metal Complexes . . . . . 301.4 Immobilised Metal Complexes as Catalysts . . . . . . . . . . . . . . . . . . . . 321.5 Metal and Supported Metal Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 371.6 Nucleophilic – Electrophilic Catalysis . . . . . . . . . . . . . . . . . . . . . . . . 391.7 Free-Radical Initiated Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . 43References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

2 Hydrosilylation of Alkynes and Their Derivatives . . . . . . . . . . . . . . . . . . 532.1 Regio- and Stereoselective Hydrosilylation of Alkynes Catalysed

by Late Transition Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 542.2 Regio- and Stereoselective Hydrosilylation of Alkynes Catalysed

by Early Transition Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 692.3 Hydrosilylation of Alkynes on Heterogeneous Catalysts . . . . . . . . . 702.4 Hydrosilylation of Alkynes in the Presence of Radical Initiators

and Lewis Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 722.5 Intramolecular Hydrosilylation of Alkynes . . . . . . . . . . . . . . . . . . . . . 74

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xvi Contents

2.6 Transition Metal-Catalysed Cyclisation/Hydrosilylationof Diynes and Enynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

3 Hydrosilylation of Carbon----Carbon Multiple Bonds in OrganicSynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873.1 Hydrosilylation – Oxidation Strategy . . . . . . . . . . . . . . . . . . . . . . . . . 883.2 Hydrosilylation – Protodesilylation Protocol . . . . . . . . . . . . . . . . . . . 1013.3 Hydrosilylation – Cross-Coupling Methodology . . . . . . . . . . . . . . . . 1083.4 Miscellaneous Advanced Synthetic Methodologies

Including Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121

4 Asymmetric Hydrosilylation of Prochiral Alkenes and TheirDerivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1254.1 Palladium-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

4.1.1 Hydrosilylation of Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . 1264.1.2 Hydrosilylation of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . 1384.1.3 Hydrosilylation of Enynes . . . . . . . . . . . . . . . . . . . . . . . . . . . 1444.1.4 Cyclisation / Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . 145

4.2 Rhodium-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1474.2.1 Hydrosilylation of Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . 1474.2.2 Hydrosilylation of Enynes and Diynes . . . . . . . . . . . . . . . . . 1474.2.3 Intramolecular Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . 149

4.3 Yttrium-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1514.4 Lanthanides-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1524.5 Miscellaneous Metal-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 1524.6 Free-Radical Initiated Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . 153References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

Part II Hydrosilylation of Carbon----Carbon Multiple Bonds in PolymerChemistry and Materials Science

5 Functionalisation and Cross-Linking of Organosilicon Polymers . . . . . 1595.1 Modified Organosilicon Polymers and Their Applications . . . . . . . . 1605.2 Silicone Curing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

6 Hydrosilylation Polymerisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1916.1 Hydrosilylation Polymerisation of Monomers Containing

C=C Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1926.1.1 Intermolecular Hydrosilylation of Alkenyl(hydro)silanes . 1926.1.2 Polyaddition of Dihydro-Substituted Organosilicon

Compounds to Organosilicon Dienes . . . . . . . . . . . . . . . . . 195

Contents xvii

6.1.3 Polyaddition of Dihydro-Substituted OrganosiliconCompounds to Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200

6.2 Hydrosilylation Polymerisation of Monomers ContainingC≡C Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2016.2.1 Intermolecular Hydrosilylation of Alkynyl(hydro)silanes . 2016.2.2 Polyaddition of Dihydrosilanes to Diynes . . . . . . . . . . . . . . 205

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

7 Functionalised (Poly)silsesquioxanes and Silicon-ContainingDendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2157.1 Functionalised Silsesquioxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2157.2 Organosilicon Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

8 Organosilicon – Organic Hybrid Polymers and Materials . . . . . . . . . . . 2418.1 Functionalisation of Unsaturated Organic Polymers

by Silicon Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2418.2 Organosilicon-Organic Multiblock and Segmented Polymers . . . . . 2468.3 Silsesquioxane-based Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . 2658.4 Surface Functionalisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

8.4.1 Material Surface Modification . . . . . . . . . . . . . . . . . . . . . . . 2758.4.2 Silicon Surface Modification . . . . . . . . . . . . . . . . . . . . . . . . . 278

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

Part III Chemo- and Enantio-Selective Hydrosilylation of UnsaturatedCarbon–Heteroatom Bonds

9 Hydrosilylation of Unsaturated Carbon----Heteroatom Bonds . . . . . . . . 2899.1 Hydrosilylation of Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . 290

9.1.1 Late Transition Metal Complexes as Catalysts . . . . . . . . . . 2909.1.2 Transition Metal Complexes of the Group 4-7 as Catalysts 3149.1.3 Main Group Metal-Based Catalysts . . . . . . . . . . . . . . . . . . . 3209.1.4 Nucleophilic-Electrophilic Catalysis . . . . . . . . . . . . . . . . . . 3209.1.5 Free-Radical Initiated Hydrosilylation . . . . . . . . . . . . . . . . . 3259.1.6 Metal and Supported Metal Catalysts . . . . . . . . . . . . . . . . . . 3269.1.7 Hydrosilylation of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326

9.2 Hydrosilylation of C=N Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3279.2.1 Transition Metal Complexes as Catalysts . . . . . . . . . . . . . . 3279.2.2 Main Group Metal-Based Catalysts . . . . . . . . . . . . . . . . . . . 3309.2.3 Nucleophilic-Electrophilic Catalysis . . . . . . . . . . . . . . . . . . 330

9.3 Hydrosilylation of C≡N Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3319.4 Hydrosilylation of Other Multiple Bonds . . . . . . . . . . . . . . . . . . . . . . 332References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333

xviii Contents

10 Asymmetric Hydrosilylation of Unsaturated Carbon–HeteroatomBonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34110.1 Asymmetric Hydrosilylation of C=O Bond . . . . . . . . . . . . . . . . . . . . 342

10.1.1 Transition Metal Complexes as Catalysts . . . . . . . . . . . . . . 34210.1.2 Main Group Metal-Based Catalysts . . . . . . . . . . . . . . . . . . . 38210.1.3 Nucleophilic-Electrophilic Catalysis . . . . . . . . . . . . . . . . . . 382

10.2 Asymmetric Hydrosilylation of C=N Bond . . . . . . . . . . . . . . . . . . . . 38410.2.1 Transition Metal Complexes as Catalysts . . . . . . . . . . . . . . 38410.2.2 Miscellaneous Metal-Based Catalysts . . . . . . . . . . . . . . . . . 38910.2.3 Nucleophilic-Electrophilic Catalysis . . . . . . . . . . . . . . . . . . 389

10.3 Asymmetric Conjugate Reduction of Nitriles, Nitroalkenesand Sulphones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399

Introduction

The name hydrosilylation (or hydrosilation) refers to the reaction of addition oforganic and inorganic silicon hydrides across multiple bonds, in particular carbon----carbon and carbon----heteroatom (i.e. carbon----oxygen and carbon----nitrogen) bondsas well as heteroatom----heteroatom (such as nitrogen----nitrogen and nitrogen----oxygen) bonds. The first example of hydrosilylation , i.e. the reaction occurringbetween trichlorosilane and 1-octene in the presence of acetyl peroxide was reported60 years ago (1947) by Leo Sommer. However, a discovery of hexachloroplatinicacid in 1957 as a very efficient precursor of the Pt-catalyst by John L. Speier hasbecome a strategic point for a wide and common application of this process as afundamental and elegant method explored over the next 50 years for laboratory andindustrial synthesis of organosilicon molecular and macromolecular compounds aswell as other organic silyl derivatives, which can also be directly subjected to or-ganic synthesis.

Although the reaction can occur by mediation of free-radicals generated in thereaction mixture, most catalysts used, predominantly transition-metal (TM) com-plexes (but also nucleophilic-electrophilic catalyst as well metal and supported met-als) accomplish the process through a heterolytic mechanism.

Scientific literature provides a number of surveys of hydrosilylation reactions orparticular aspects of these processes, including general reviews, chapters or booksand articles reviewing special problems related to this process. The surveys thatappeared before 1990 (44 references in total) have been listed in our previous bookentitled “Comprehensive Handbook on Hydrosilylation”, published in 1992 [1].

That handbook consists of two basic parts. The first part of that book presents thetypes of catalysts used in the process (Chapter 2), the structures of organic (Chap-ter 3) and silicon hydride (Chapter 4) substrates, discussed from the point of viewof the reaction mechanism and from that of the evaluation of the optimum condi-tions necessary for the synthesis of organosilicon compounds and organic deriva-tives of silicon. Two additional chapters focus on the hydrosilylation of unsaturatedorganosilicon compounds (Chapter 5) and application of these processes in synthe-sis of silane coupling agents, reduction of organic compounds and modification ofpolymers (Chapter 6). The second part of our handbook presenting the details of thereaction conditions, products and yields and/or selectivity was edited in the tabulated

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xx Introduction

form and for selected trisubstituted silanes the references were chosen from morethan 2100 papers and patents published from 1965 to early 1990.

The aim of the present book is to supply a comprehensive review of the recentadvances in all aspects of the hydrosilylation processes and their direct applicationcovering the literature data that appeared over the last 18 years, i.e. 1990–2007.

This monograph includes also general reviews, chapters as well as individualreview articles related to the hydrosilylation processes published in the last twodecades, which are listed separately in the References under the heading [1–39].The reader should note however, that these reviews attempting to provide a compre-hensive coverage of literature were published usually some time ago.

Extensive reviews of literature in the field was provided by Ojima [2, 5] as wellas by Lukevic’s and Voronkov’s group [3]. Concise accounts covering important as-pects of the reaction have been published by Brook [7] and Reichl and Berry [6]. Ourcontribution to this field after [1] (1992) was concentrated on the hydrosilylationof carbon----carbon multiple bonds as an efficient method for obtaining organosil-icon molecular and macromolecular products, approached from the point of viewof catalysis, which is fundamental for the hydrosilylation reactions [4, 8, 9, 12, 14].Individual aspects of the reaction initiated by free radicals were addressed by Chat-gilialoglu et al. [10]. Trost and Ball provided a general overview of the alkynehydrometallation including synthetic and mechanistic aspects of alkyne hydrosi-lylation [11]. A brief review covering the literature published since 1990 throughmid 2005 on the significant advances from the viewpoint of homogeneous catalysismade by Roy appeared when we were completing this book [13].

Advances in asymmetric hydrosilylation of olefins, carbonyl derivatives andimines achieved in 1990s were reviewed by Nishiyama and Itoh [15]. Hayashi re-viewed the catalytic and synthetic aspects of hydrosilylation of linear and cyclicolefins and dienes [16, 17]. Additionaly in a number of accounts Hayashi high-lighted the progress in development of the family of chiral monodentate phosphineligands (MOP) and their application in palladium catalysed asymmetric hydrosi-lylation of wide variety of olefins [18–20]. Accounts summarising the design ofsilicon-stereogenic silanes and their application in asymmetric catalysis includinghydrosilylation were recently provided by Oestreich [21, 22].

Problems concerning the hydrosilylation processes in polymer chemistry andmaterial science were discussed in most of the abovementioned reviews as wellas others concentrating only on polymers [23, 24]. Some classes of functionalisedsilicones, on account of their practical importance, like fluorosiloxanes [25] liquidcrystalline polysiloxanes [26] and silicone polyethers [27], were discussed sepa-rately.

Modifications of organic polymers with organosilicon compounds were reviewedby Grath and Tremont [28]. Synthesis and properties of silicon-containing den-drimers including hydrosilylation were the subjects of the review by Majoral andCaminade [29]. Functionalisation of silsesquioxanes via hydrosilylation [30,31] andproduction of new composite materials [32] were also presented.

Gonzalez and Nolan provided a general overview of the application of metalcatalysed hydrosilylation (including the asymmetric hydrosilylation) of carbonyl

Introduction xxi

compounds covering the period (1999–2006) [33] followed by their very recentreview of the reaction catalysed by copper, silver and gold complexes [34]. Devel-opment of copper catalysed 1,2- and 1,4-hydrosilylation was reviewed by Oestre-ich [35]. In a numer of reviews Nishiyama summarises the catalytic and syntheticaspects of asymmetric hydrosilylation of carbonyl and imine compounds [36, 37].Advances in asymmetric hydrosilylation of carbonyl compounds and imines werereviewed by Carpentier and Riant who focused on the new catalytic systems andmechanistic aspects of the reaction as well as the new synthetic opportunities[38, 39].

In view of extensive development of research work concerning hydrosilyla-tion of carbon----carbon multiple bonds on the one hand, as well as unsaturatedcarbon----oxygen and carbon----nitrogen bond, on the other, and application of cat-alytic hydrosilylation in asymmetric synthesis as well especially in polymer chem-istry and materials science, this monograph was divided into three parts.

Part I presents all aspects of hydrosilylation of carbon----carbon multiple bonds.Various catalytic systems which are the basis of hydrosilylation of C=C bonds(Chapter 1) and C≡C bonds (Chapter 2) are discussed from two points of view:elucidation of the mechanisms of catalysis and finding the optimum conditionsnecessary for synthesis of organosilicon compounds. While in Chapter 1 more in-formation is given on new catalysts leading to most effective synthetic routes oflaboratory and industrial importance, regarding saturated organosilicon products,the hydrosilylation of alkynes (Chapter 2) is at the moment the most powerful andatom-economical approach for stereo- and regio-selective synthesis of alkenylsi-lanes. The latter are versatile building blocks in organic synthesis. The develop-ment of sequential processes including hydrosilylation of functionalised alkenesand alkynes as the initial step through the respective organosilicon intermediates hasbeen further enhanced by several protocols for converting the silyl group into otherfunctional groups. Thus in Chapter 3 advanced synthetic methodologies includinghydrosilylation (one-pot processes) are summarised. Part I is completed by a review(Chapter 4) of asymmetric hydrosilylation of alkenes and alkadienes in the presenceof chiral catalysts, which leads to synthesis of enantioenriched alkylsilanes and al-lylsilanes, respectively, or (if followed by oxidation) to the corresponding chiralalcohols.

The hydrosilylation processes, particularly of carbon----carbon multiple bonds,that have been in the last two decades extensively applied in the field of polymerchemistry and material science are described. Part II of the present book. The appli-cations discussed in Chapter 5 employ the functionalisation of oligo- and polysilox-anes with Si----H bonds, which leads to reactive silicones, being the most attractivesilicone materials for adhesives, binders, sealents, optical coating, dielectric coat-ing and a lot of more applications. Catalytic cross-linking of polysiloxanes via theaddition of polyfunctional silicon-containing hydride to poly(vinyl)siloxane lead-ing to silicon rubber is also discussed in Chapter 5. The catalytic hydrosilylationof difunctional organosilicon monomers containing alkenyl (alkynyl) and/or Si----Hbond leading to formation of saturated (unsaturated) organosilicon polymers bearingthe Si----C (Si----C=) bonds is the subject of Chapter 6. While saturated polycarbosi-

xxii Introduction

lanes and related polymers are applied in heat resistant and moulding materials,silicon-containing �-� conjugated polymers such as poly(silylene, vinylene)s orpoly(arylene, silylene,vinylene)s can be of great importance as optoelectronic ma-terials.

Functionalised (poly)silsesquioxanes and silicon-containing dendrimers synthe-sised via hydrosilylation procedures are described in Chapter 7. There is now asignificant interest in both types of nanoscaled macromolecules with a particulararchitecture and their potential application as precursors of new materials and espe-cially in the processing of composites.

Chapter 8 regards the application of hydrosilylation in the synthesis of hybridorganic-inorganic materials via functionalisation of unsaturated organic polymer bysilicon compounds, and by multifunctionalised crosslinking reagents containing Si-H and vinyl groups as well as using functionalised silicon-containing dendrimers.Silsesquioxane-based nanocomposites materials are discussed in a separate Sub-chapter 8.3. Finally, the information on the surface modification of polymers as wellas other materials, particularly silicon element via hydrosilylation to improve theirhydrophilicity or hydrophobicity completes Chapter 8. All hydrosilylation processesutilised in the synthesis of polymers and (nano)materials occur predominantly in thepresence of Pt-catalyst (usually Pt-Karstedt’s catalyst or other platinum complexesor Pt/C catalyst).

Part III deals with the hydrosilylation of unsaturated carbon----heteroatom bond,mostly C=O and C=N (but also C≡N, N=N and N=O) bonds as a catalyticmethod for the reduction of C=O and C=N bonds - one of the most fundamen-tal transformations in organic chemistry (Chapter 9). Both 1,2-hydrosilylation ofcarbonyl compounds or imines and 1,4-hydrosilylation of �,�-unsaturated systemswere described. A separate section is devoted to the hydrosilylation of CO2. Cat-alytic hydrosilylation of prochiral ketones and imines with substituted silanes andsiloxanes which can provide (if followed by hydrolysis) convenient access to chiralalcohols and amines is discussed from the catalytic and synthetic point of view inChapter 10. Contrary to the procedures used in the synthesis of hybrid inorganic-organic polymers and materials, the hydrosilylation of C=O and C=N bonds canproceed in the presence of other then Pt-complex catalysts as discussed in detail inChapters 9 and 10.

Acknowledgments The preparation of this book would have been impossible without the kindand great effort of many colleagues and Ph.D. students of Faculty of Chemistry, Adam MickiewiczUniversity. We want to express our appreciation to Professors Ryszard Fiedorow, Jacek Gawronskiand Jacek Gulinski for reading individual chapters and correcting errors. Special words of thanksgo to Mrs Teresa Nowicka and Mrs Anna Macina for Their invaluable assistance.

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Introduction xxiii

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