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 Advances in
ORGANOMETALLIC CHEMISTRY
VOLUME 55
This page intentionally left blank
 Advances in
Organometallic
Chemistry
EDITED BY

ROBERT WEST ANTHONY F. HILL

ORGANOSILICON RESEARCH SCHOOL OF CHEMISTRY,
RESEARCH CENTER INSTITUTE OF ADVANCED STUDIES,
DEPARTMENT OF CHEMISTRY, AUSTRALIAN NATIONAL UNIVERSITY
UNIVERSITY OF WISCONSIN, CANBERRA, ACT
MADISON WI, USA AUSTRALIA

MARK J. FINK
DEPARTMENT OF CHEMISTRY
TULANE UNIVERSITY
NEW ORLEANS, LOUISIANA, USA

FOUNDING EDITOR
F. GORDON A. STONE

VOLUME 55

Amsterdam  Boston  Heidelberg  London  New York  Oxford  Paris

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Academic Press is an imprint of Elsevier PRESS
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08 09 10 11 12 10 9 8 7 6 5 4 3 2 1
 Contents

CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

PREFACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

A Review of Recent Progress in Catalyzed Homogeneous

Hydrosilation (Hydrosilylation)
AROOP K. ROY

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
II. Hydrosilation with Iron Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 2
III. Cobalt Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
IV. Nickel-Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
V. Group IVB, Group IIIB, Lanthanides and Actinides . . . . . . . . . . . . . . . . 16
VI. Manganese, Rhenium and Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
VII. Catalysis by Acids, Bases, or Free Radicals. . . . . . . . . . . . . . . . . . . . . . . 22
VIII. Asymmetric Hydrosilation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
IX. Applied aspects – Synthesis of Polymers and Materials . . . . . . . . . . . . . . 32
X. Mechanistic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
XI. Challenges and the Future of Hydrosilation . . . . . . . . . . . . . . . . . . . . . . 50
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

Organotransition Metal Complexes for Nonlinear Optics

JOSEPH P. MORRALL, GULLIVER T. DALTON,
MARK G. HUMPHREY and MAREK SAMOC

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
II. Theory and Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
III. Molecular Second-Order Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
IV. Molecular Third-Order Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
V. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Appendix: Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

v
vi Contents

Pentadienyl Complexes of the Group 4 Transition Metals

LOTHAR STAHL and RICHARD D. ERNST

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
II. Bis(Z5-pentadienyl)Metal Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
III. Mono(Z5-pentadienyl)Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
IV. Miscellaneous Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
V. Reaction Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
VI. Future Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

Mixed Metal Acetylide Complexes

PRADEEP MATHUR, SAURAV CHATTERJEE and VIDYA D. AVASARE

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
II. Mixed Group 8 Metal Acetylide Complexes . . . . . . . . . . . . . . . . . . . . . . 202
III. Mixed Group 10 Metal Acetylide Complexes . . . . . . . . . . . . . . . . . . . . . 207
IV. Mixed Group 11 Metal Acetylide Complexes . . . . . . . . . . . . . . . . . . . . . 210
V. Mixed Group 6–9 Metal Acetylide Complexes. . . . . . . . . . . . . . . . . . . . . 213
VI. Mixed Group 10–12 Metal Acetylide Complexes . . . . . . . . . . . . . . . . . . . 250
VII. Other Mixed Metal Acetylide Complexes . . . . . . . . . . . . . . . . . . . . . . . . 255
VIII. Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273

Transition Metal Organometallic Synthesis Utilising

Diorganoiodine(III) Reagents
ALLAN J. CANTY, THOMAS RODEMANN and JOHN H. RYAN

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
II. Mechanisms of Reactions of Diorganoiodine(III) Reagents. . . . . . . . . . . . . . 281
III. Organometallic Chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
IV. Summary and Emerging Opportunities in Organometallic Chemistry . . . . . . . 307
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308

INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
CUMULATIVE LIST OF CONTRIBUTORS FOR VOLUMES 1–36 . . . . . . . . . . . . . . 321
CUMULATIVE INDEX FOR VOLUMES 37–55 . . . . . . . . . . . . . . . . . . . . . . . . . . 325
 Contributors
Numbers in parentheses indicated the pages on which the authors’ contributions begin.
VIDYA D. AVASARE (205), Chemistry Department, Indian Institute of Technology-
Bombay, Powai, Bombay, India
ALLAN J. CANTY (283), School of Chemistry, University of Tasmania, Hobart, Tasmania,
Australia
SAURAV CHATTERJEE (205), Chemistry Department, Indian Institute of Technology-
Bombay, Powai, Bombay, India
GULLIVER T. DALTON (63), Department of Chemistry, Australian National University,
Canberra, ACT, Australia and Laser Physics Centre, Research School of Physical
Sciences and Engineering, Australian National University, Canberra, ACT, Australia
RICHARD D. ERNST (139), Department of Chemistry, University of Utah, Salt Lake City,
UT, USA
MARK G. HUMPHREY (63), Department of Chemistry, Australian National University,
Canberra, ACT, Australia
PRADEEP MATHUR (205), Chemistry Department, Indian Institute of Technology-
Bombay, Powai, Bombay, India
JOSEPH P. MORRALL (63), Department of Chemistry, Australian National University,
Canberra, ACT, Australia and Laser Physics Centre, Research School of Physical
Sciences and Engineering, Australian National University, Canberra, ACT, Australia
THOMAS RODEMANN (283), School of Chemistry, University of Tasmania, Hobart,
Tasmania, Australia
AROOP K. ROY (1), Personal Care and Pharmaceuticals R&D, Noveon (A Subsidiary of
The Lubrizol Corporation), Cleveland, OH, USA
Current Affiliation: Performance Additives – Personal Care, Wacker Chemical Corpora-
tion, Adrian, MI, USA.
JOHN H. RYAN (283), CSIRO Molecular and Health Technologies, Ian Wark Laboratory,
Bayview Avenue, Clayton, Vic., Australia
MAREK SAMOC (63), Laser Physics Centre, Research School of Physical Sciences and
Engineering, Australian National University, Canberra, ACT, Australia
LOTHAR STAHL (139), Department of Chemistry, University of North Dakota, Grand
Forks, ND, USA

vii
This page intentionally left blank
 Preface
With this volume, Mark Fink officially joins us as Editor. Mark is Professor of Chemistry
at Tulane University, where he leads a diversified program of research on multiply bonded
and low-coordinate silicon and germanium compounds, palladium–silicon compounds in
catalysis, and precursor molecules, especially of gallium, for CVD processing. He is a pioneer
in the study of organosilicon compounds in molecular beams. His perspective on main group
chemistry, and the interface with transition-metal chemistry and applications, ideally places
him to maintain the synergy between main-group and transition-metal organometallic
chemistry that Advances in Organometallic Chemistry has endeavored to chronicle. It is a
pleasure to welcome Mark to our editorial team.

Anthony F. Hill and Robert West

ix
This page intentionally left blank
 A Review of Recent Progress in
Catalyzed Homogeneous
Hydrosilation (Hydrosilylation)
 AROOP K. ROY
Personal Care and Pharmaceuticals R&D, Noveon (A Subsidiary of The Lubrizol Corporation),
9911 Brecksville Road, Cleveland, OH 44141, USA
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
II. Hydrosilation with Iron Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
III. Cobalt Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
IV. Nickel-Triad Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
V. Group IVB, Group IIIB, Lanthanides and Actinides . . . . . . . . . . . . . . . . . . . . . . . . 16
VI. Manganese, Rhenium and Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
VII. Catalysis by Acids, Bases, or Free Radicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
VIII. Asymmetric Hydrosilation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
IX. Applied Aspects – Synthesis of Polymers and Materials . . . . . . . . . . . . . . . . . . . . . . 32
X. Mechanistic Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
XI. Challenges and the Future of Hydrosilation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

I
INTRODUCTION

Without a doubt, amongst silicon–carbon as well as other silicon-heteroelement

bond-forming reactions, the catalyzed hydrosilation (or hydrosilylation) reaction is
the most fascinating chemical transformation. Even for a specialized chemical re-
action, the steady periodic reviews that have appeared over the last 30 years on the
subject are clear testimony to the diverse and continuing utility of this reaction in
organic, inorganic, bio-organic, organometallic, polymer and materials chemistry.
The last extensive review of published literature in the area (covering research
through about 1996) was provided as recently as 1998 by Ojima and coworkers.1
This, together with Ojima’s earlier review2 and the treatise by Marciniec,3 con-
sidered by many as the ‘‘Bible’’ on hydrosilation, chart the history of developments
in the area in compelling detail, since Speier’s,4 Voronkov and coworkers’5 and
Harrod and Chalk’s6 descriptive accounts of the reaction covering the first two
decades of explosive growth appeared in the late 1970s. An account that is concise
yet which covers all of the important aspects of the reaction has been provided by
Brook.7 Marciniec also recently reviewed CQC and CRC hydrosilation.8
The aim of this brief review, covering literature only since 1990 up through ca.
mid-2005, is to update the readership and the practicing scientist on some of the
significant advances that have been made in the field. These have occurred

Corresponding author. Present affiliation: Performance Additives – Personal Care, Wacker Chemical
Corporation, 3301 Sutton Road, Adrian, MI 49221, USA.
E-mail: [email protected] (A.K. Roy).

ADVANCES IN ORGANOMETALLIC CHEMISTRY r 2008 Elsevier Inc.

VOLUME 55 ISSN 0065-3055/DOI 10.1016/S0065-3055(07)55001-X All rights reserved.
2 A.K. ROY

particularly in areas such as new ligands for catalysts, the range of transition metal
species that effectively catalyze the reaction, asymmetric hydrosilation, significant
growth in application to a plethora of new polymer and materials synthesis and,
most notably, strides in unraveling the inner workings of the catalytic cycle. In this
last context, the terms precatalyst and catalyst have been used interchangeably in
this review to denote starting compounds or complexes that facilitate hydrosilation.
The word combination ‘‘true catalyst’’ has only been used where the actual catalytic
species has been positively identified.
To preview the progress in the field, completely new ligand classes such as dii-
mines and N-heterocyclic carbenes have surfaced; several lanthanides are estab-
lished as quite effective catalysts; asymmetric hydrosilation is now an extremely
important tool in chiral synthesis; materials accessed via hydrosilation range from
new block copolymers to POSS-based composites and dendrimers, and evidence is
substantial that more than one type of catalytic cycle is operative for different
transition metals or groups of transition metals and perhaps even for different
oxidation states of some metals.
The author’s association with industrial hydrosilation processes and research for
a number of years has been particularly enlightening in connection with several
commercially important reactions and their nuances, oddities and challenges. This
has helped the development of certain perspectives on the reaction which will un-
doubtedly infiltrate parts of this review. It is hoped that these occasional views will
enhance the value of this chapter to the readership. Also, because Ojima’s second
review was published fairly recently there will be overlap of coverage. However, the
organization of this review is not as elaborate and it will only cover hydrosilation
occurring, intended to occur or perceived to occur in homogeneous media, except
for brief but important comparisons with and discussion on some new develop-
ments in the area of heterogeneous catalysis.

II
HYDROSILATION WITH IRON TRIAD CATALYSTS

Amongst the Fe-triad metals Fe, Ru and Os, only a few hydrosilations have
been reported using the first and third row metal catalysts. Very recently, however,
a new type of Fe(0) complex, containing a diimine-based pincer ligand, and also
containing two coordinated dinitrogen molecules was shown to be an effective
and, remarkably, regiospecific catalyst for the hydrosilation of a variety of
terminal alkenes with PhSiH3 or Ph2SiH2. For example, styrene which generally
leads to both terminal and internal adducts, produced only the terminal hydros-
ilation product [Eq. (1)], as did all other terminal alkenes examined.9 The novel
iron complex was also highly successful in catalyzing the hydrosilation of diphenyl
acetylene with phenylsilane to produce a monosilylated product. This unique
activity for an iron complex, the few previous examples of which have been
known to be poor hydrosilation catalysts, suggests that modulation of metal
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 3

activity using newly designed ligands may allow the synthesis of newer and
much more effective catalysts from transition metals that are less expensive than
the traditional Pt or Rh-based complexes. The observed high lability of N2 lig-
ands in 1 and the isolation of both Z2-SiH and p-alkyne complexes via displace-
ment of N2 afford valuable insight on the catalytic activity of this unusual iron
complex.

SiH2Ph
"Fe"
+ PhSiH3

Exclusive β-adduct
(1)
N
"Fe" = Ar = 2,6-iPr2-C6H3
N Fe N
Ar Ar
N2
N2
1
Ruthenium complexes are particularly effective for the hydrosilation of alkynes.
A variety of terminal as well as internal alkynes have been hydrosilated in respect-
able to excellent yields using a number of catalyst types. With 5 mol% [RuCl2(p-
cymene)]2 as catalyst, stereroselectivities upwards of 95:5::Z:E and yields in the
range 78–98% are achieved for many terminal alkynes, including several containing
functional groups.10 Interestingly, a regioselectivity reversal to high a-product is
observed for alkynes with a hydroxyl group a- or b- to the internal alkyne carbon,
but not for this substituent at the g position or beyond or for a benzylated hydroxyl
group. For complexes with phosphine ligands, basicity of the phosphine plays a
dominant role in stereoselectivity and overall product distribution. This has been
nicely demonstrated by Ozawa and coworkers.11 With Ph3P ligands and tertiary
arylsilanes, 499:1 E selectivity was observed for a number of terminal alkynes,
whereas a Ru–Si complex with Pri3P ligands and a Ru-complex with Cy3P in place
of Ph3P afforded Z-products, in most cases with selectivity 490:10 [Eq. (2)]. Fur-
ther, overall products yields were mostly 496%. Such phosphine-substituent effects
were also reported by Oro and coworkers.12 Both groups propose mechanistic
pathways to the products that incorporate similar intermediates, but Oro’s group
also postulates the involvement of polynuclear hydride-bridged Ru complexes as a
key factor in the stark selectivity differences. It appears from the electronic char-
acter of the silanes used by the two groups that the silane substituents also exert
some effect on the stereoselectivity. In fact, the effect of various silanes on product
distribution (which includes enyne formation) with RuCl2(PPh3)3 has been re-
ported.13 Nevertheless, since the product vinylsilanes can be of further utility in
various organic transformations, simple phosphine ligand substitution offers a
convenient way to arrive at ultimate products with different geometries or isomeric
identities.
4 A.K. ROY

R + HSiR'3
PPh3 PPri3
OC H OC
Ru Ru SiMe2Ph
Ph3P Cl Cl
PPh3 PPri 3
2 3 (2)
R H

H SiR'3 R SiR'3

E Z

Unlike the high anti-Markovnikov or b-selectivity exhibited by the above neutral

phosphine complexes, cationic Ru complexes have been reported to provide high
regioselectivity towards Markovnikov adducts (in good to high yields) for both
terminal and internal alkynes.14 More fascinating still is the use of Grubbs’ first-
generation olefin-metathesis catalyst [RuQCHPhCl2(PCy3)2] that yields adducts
with regio- or stereoselectivity based on the nature of the alkyne and the silane.15
Although many metal-carbonyl clusters technically do not fall in the category of
homogeneous catalysts, several substituted ruthenium-carbonyl clusters are soluble,
and Ru3(CO)12 has been shown to behave in some cases as if lower nuclearity
fragments derived from it are the catalytic species in hydrosilation reactions. The
hydrosilation of allyl chloride is an important industrial reaction that is also
wrought with side reactions. This will be addressed in a later Section XI but
Ru3(CO)12 is one of a few catalysts that provide yields of useful 3-chloropropylsi-
lanes in excess of 70% via hydrosilation of allyl chloride. Using a one to three fold
molar excess of HSi(OMe)3 over allyl chloride at 80 1C, 470% yield of
chloropropyltrimethoxysilane was obtained by Tanaka and coworkers.16 A m-silane
diruthenium complex 4 catalyzes the hydrosilation of imines and ketones with
secondary silanes via cooperative action between the ruthenium centers.17 A novel
catalytic hydrosilation of esters using either Ru3(CO)12 or [RuCl2(CO)3]2, in the
presence of diethylamine and ethyl iodide as co-catalysts, leads to aldehydes in good
to excellent yields following hydrolysis of the alkyl silyl acetals. Many other TM
carbonyl clusters were inactive in this reaction.18
R R
Si
H H CO
CO
HR2Si Ru Ru SiR2H
OC OC
Ph2P PPh2

A few osmium complexes are active catalysts for the hydrosilation of phenyl-
acetylene with Et3SiH. Whereas ½RuHClðCOÞðPPri3 Þ2  is stereospecific in providing
Z-selectivity as well as quantitative yield, the corresponding Os complex yields high
Z-adduct or E-adduct depending on whether a stoichiometric amount or excess
silane, respectively, is used.19 Some other examples of Os complexes have also been
reported for the hydrosilation of phenylacetylene with Et3SiH.20
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 5

III
COBALT TRIAD CATALYSTS

Unlike the iron triad complexes, cobalt triad compounds, particularly those of
Rh and Ir are much more active in hydrosilation catalysis, although the cobalt
carbonyl Co2(CO)8 has played a very important role in furthering understanding of
the catalytic cycle with transition metals. Recently, a simple cobalt salt, CoBr2,
in conjunction with added Bun3P, ZnI2 and Bu4NBH4 was shown to afford
1,4-hydrosilated isoprene (silicon at C-4) in 90% isolated yield, where most
metal catalysts derived from Ru, Rh, Pd and Pt usually lead to a mixture of
regioisomers.21
Mixed Co–Rh carbonyl clusters have been reported by Ojima and coworkers to
catalyze hydrosilations of 1-hexyne, isoprene, cyclohexanone and cyclohexenone
[Eq. (3)] and compared against catalysis by Rh4(CO)12, Wilkinson’s catalyst and
Co2(CO)8.22 Stereoselectivity mostly in the range 85–95% towards the Z-adduct
was obtained with 1-hexyne under various and often mild conditions, although
some E-adduct and Markovnikov product were always present, except in the case of
Co2(CO)8 which gave no Z-adduct. Lower levels of catalyst led to higher cis/trans
product ratios. Silane substituents also affected product distribution, with alkyl-
and alkyl/aryl silanes providing high Z product isomer, and alkyl/chloro and
alkoxysilanes leading to E- and a-adduct only. For isoprene hydrosilation, product
selectivity toward 1-silyl adduct was high for all clusters, except Co2(CO)8 which
again differed from the rest in affording a high 4-silyl adduct. It is of interest to note
that although the Rh catalysts are different, Ojima proposed a selectivity mech-
anism that incorporates an isomerization on the Rh complex that leads from an
E-alkene to a Z-alkene, while Hiyama and coworkers recently suggested an
isomerization catalyzed by RhI(PPh3)3 and heteroatom-substituted hydrosilane
that converts Z-alkenylsilanes to the E-isomers.23 The latter was not observed with
RhCl(PPh3)3 in Ojima’s study with Et3SiH as the hydrosilane.

Substrate-, Silane-,
Catalyst-dependent
Catalyst Hydrosilation Product:
Hydrosilane stereo-, regioisomer
O O (and silylenolether) (3)

Catalysts studied: Rh4(CO)12, Co2Rh2(CO)12, Co3Rh(CO)12, Co2(CO)8, RhCl(PPh3)3.

Silanes examined: Et3SiH, Et2MeSiH, EtMe2SiH, PhMe2SiH, Ph2SiH2, ClMe2SiH,
Cl2MeSiH, (MeO)3SiH. Not all catalysts or silanes investigated for all substrates.

In the context of bimetallic catalysts, an unusual cationic Ti–Rh bimetallic com-

plex 5 exhibits an interesting cooperative effect in catalyzing the hydrosilation of
acetophenone with Ph2SiH2.24 A weak bonding interaction between rhodium and a
Cl on titanium apparently stabilizes a lower-valent Rh intermediate such that the
bimetallic complex delivers a much higher hydrosilation yield than the correspond-
ing Rh(COD) monometallic complex based on 1,2-bis(diphenylphosphino)benzene.
6 A.K. ROY

The Ti is thought not to be directly involved, since Cp2TiCl2 does not catalyze this
reaction.

PPh2
Rh(COD)
PPh2
Ti Cl
Cl
OTf -

Takeuchi and coworkers discovered that stereoselectivity in 1-alkyne hydrosilat-

ion can be very effectively controlled via solvent and catalyst choice with Rh com-
plexes, and have reported extensively on functional and non-functional 1-alkyne
hydrosilations (in excellent yields) and the utility of adducts in further transfor-
mations.25 For example, 1-hexyne hydrosilation with Et3SiH in EtOH or DMF
using [RhCl(COD)]2 leads to high Z-selectivity, whereas in nitrile solvents, in the
presence of added Ph3P, the same Rh dimer precatalyst affords very high E-selec-
tivity. The high E-selectivity is explained by invoking a ‘‘near-naked’’ cationic
complex derived from [Rh(COD)2]BF4/2PPh3, where only high cationic character
leads to high trans-adduct (using BPh4 as the counter anion gave the Z-isomer as
the major product). In contrast to the findings above, Basato and coworkers report
an unusual oxothioether and acetato ligated cationic dirhodium complex, with the
same BF 4 counterion, [Rh2(m-OAc)3(RSCH2Z)]BF4 {RQMe, Ph; ZQC(O)OEt,
CH2C(O)OMe}, leads to high Z-selectivity (62% conversion) for the hydrosilation
of 1-hexyne with PhMe2SiH.26 Similarly, for the hydrosilation of phenylacetylene
with triphenyl-, triethoxy- or triethylsilane, Faller and D’Alliesi report high E or Z
selectivity and little or no a-adduct depending on whether the catalyst is
[RhCp*(BINAP)](SbF6)2 or [RhCl2Cp*]2, respectively.27 Such dramatic changes
in product selectivity as reported by these groups underscore the effect of electronic
and steric changes in a metal’s coordination sphere on its catalytic behavior, al-
though such effects are often not predictable. With Wilkinson’s catalyst
[RhCl(PPh3)3], the reaction of styrene with Ph2SiH2 yields only the b-adduct and
other side products, but no a-adduct: whereas PhSiH3 is unreactive towards styrene
at room temperature but yields the E-adduct exclusively with phenylacetylene as the
substrate.28
Recently, zwitterionic Rh complexes 6 were reported to be interesting hydros-
ilation catalysts.29 The complexes, similar to the cationic rhodium
[Rh(P–P)(solv)2]+ of Osborne and Schrock, though less active than the corre-
sponding cationic complexes, provide only the beta-adduct from the hydrosilation
of styrene with Ph2SiH2. Further, unlike the cationic complexes the zwitterionic
compounds are highly tolerant of coordinating solvents like acetonitrile and are
appreciably soluble in non-polar hydrocarbons such as benzene.
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 7

R2
E L
B Rh
E L
R2

6
E = P, R = phenyl;
E = N, R = methyl

One of the newer developments in catalytic chemistry is performing multiple,

distinct transformations in a ‘‘one-pot’’ fashion, using one or more catalysts. Tan-
dem hydrosilation-cyclizations have been reported for a number of catalysts, in-
cluding the relatively new class of catalysts based on NHC (N-heterocyclic carbene)
ligands.30–36 Of the metal compounds that have been utilized, Rh complexes are the
catalysts of choice for these reactions. Reported research in the area covers a
plethora of unsaturated substrates, including enynes, diynes, allenynes, enediynes
and triynes, with many containing heteroatoms that allow the construction of he-
terocycles from acyclic starting materials. The number of publications in the area of
generating carbocycles and heterocycles in the last 15 years, for ‘‘silylcarbocyclizat-
ion’’ alone, are too numerous to cover in detail within the scope of this review.
Hence, a select few are represented in [Eqs. (4)–(8)]. The use of hydrosilation of
ynals as a synthetic tool for the generation of allenes has also been reported.37
O OSiEt3 OSiEt3
1% RhCl(PPh3)3
H CO2Me CO2Me
+ (4)
Et3SiH
CO2Me
toluene,50oC 42-81%

R
Rh(acac)(CO)2
R
(MeO)3SiH (2/5 mol%) H
Z + or Z
o SiR'3
(EtO)3SiH toluene, 60 C
. CO (1 atm) (5)
(3 equiv)

Z = TsN, O, (EtO2C)2C; R = Me, n-Bu, Ph 46-82%

N N
Bu R
R Rh(COD)Cl SiEt3(SiMe2Ph)
Z Z
Et3SiH or PhMe2SiH (6)
CH2Cl2, reflux
34-90%

Z = TsN, (MeO2C)2C, (EtO2C)2C, O, (MeOC)2C, Me2C(OC)2C; R = Me, Bu, Ph

8 A.K. ROY

PPh2
Rh BF4
PPh2
R
R
[Rh(BINAP)(COD)]+BF4- SiEt3 (7)
Z Z
R Et3SiH(or Me2EtSiH or Ph2MeSiH)
DCE, 70 oC
31-73%

Z = TsN, O, (MeO 2C)2C, (R'O)2C; R = Me, other combinations; R' = Me, Bn, etc.
Not all Z, R, R' combinations examined.

Rh- or
EtO2C (Rh-Co)carbonyl EtO2C SiR3 EtO2C SiR3
+
EtO2C R3SiH, CO (1 atm) EtO2C EtO2C CHO
(8)
Excellent yields Minor to negligible

R3 = Me2Ph, Ph2Me, (EtO)3, (EtO)2Me, (MeO)3, Ph3, tBuMe2. Not all silanes used
with all catalysts.

For both acyclic and cyclic a,b-unsaturated ketones and in general for a,b-
unsaturated carbonyl compounds such as aldehydes and esters, [Rh(OH)(COD)]2 is
a more efficient catalyst than other types of Rh(I) catalysts.38 Products are obtained
quickly in excellent yields under mild conditions (often at r.t.) and acyclic substrates
afford E/Z ratios from 2:1 to 4:1. Crabtree and Rivera investigated the effect of
hydrogen bonding on catalytic activity of specially designed NHC complexes of Rh,
and report that a strategically placed amide group on the ‘‘wing tip’’ of the carbene
ligand significantly alters selectivity in the hydrosilation of PhCHQCHCOMe with
Et3SiH (that can lead to four different products).39 Methodically run elimination
experiments lead to their proposal that H-bonding is involved in the transition state
for hydrosilation between the substrate and the catalyst.
For application toward the construction of peptidomimetics, Sieburth and co-
workers studied the hydrosilation of Boc-protected enamines with a variety of
silanes, using Rh2(OAc)4.40 Exclusive a-selectivity leads to the protected a-amino
silanes which are readily deprotected with TFA. However, the yield is dependent on
both silane and alkene substituents.
The use of a bowl-shaped phosphine, with three terphenyl groups that are 2,6-
methyl-substituted on the outer rings, P(tm–tp)3, as an added ligand to
[{RhCl(C2H4)2}2] dramatically increases the Rh dimer’s catalytic activity toward
the hydrosilation of cyclohexanone and other ketones, when compared to many
other bulky and non-bulky phospines with tertiary silanes.41 Marciniec and
coworkers have reported monomeric and dimeric siloxy-rhodium complexes,
[Rh(OSiMe3)(PCy3)(cod)] and [{Rh(m-OSiMe3)(diene)}2], that exihibit high activ-
ity in the hydrosilation of allyl glycidyl ether and 1-hexene respectively.42 The
dimeric SiO–Rh complex was found to be much superior to the corresponding
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 9

Cl–Rh dimer. Stoichiometric reaction of hydrosilanes with both catalysts indicated

the formation of hydridorhodium intermediates and the absence or low-level for-
mation of dehydrogenative silylation products is suggestive of a Chalk–Harrod
mechanistic pathway for the catalysis.
Recently, a comparison of the catalytic efficacy of Rh(I), (II) and (III) complexes
against Karstedt’s catalyst was made, since Rh is the most effective metal following
Pt for hydrosilation reactions but Pt is most often used for commercial processes.43
Both a model reaction, hydrosilation of 1-octene with triethoxysilane, and a com-
mercially useful reaction, hydrosilation of allyl alcohol ethoxylate with poly
(dimethyl-co-methylsiloxane) were studied, with respect to rate of reaction and
terminal vs. internal addition of SiH. Amongst the various phosphine-based and
one non-phosphine-based Rh complexes examined, none fared well against
Karstedt’s catalyst over a 4- and 13-hour reaction period in refluxing toluene,
except [Rh(CO)(PPh3)(Tp)] {Tp ¼ tris(pyrazolyl)borate}, which was comparable in
yield and selectivity. For the polymer reaction, again only a Tp–Rh complex,
[Rh(CO)2(Tp)], compared favorably in rate but not in selectivity. Rh(II) and (III)
complexes were totally outperformed by Karstedt’s catalyst in the study.
Heterogeneous catalysts wield a particular superiority over the homogeneous
type, especially in industrial processes – they are often easily separated from prod-
ucts and reused, although they also have disadvantages including lower activity
compared to the ‘‘soluble’’ catalysts. Thus, chemists and chemical engineers alike
are increasingly interested in harnessing this advantage for homogeneous catalysts
which offer them versatility in many more ways. For hydrosilation, reports have
recently appeared on progress in this area that takes advantage of the solubility
properties of fluorocarbon-groups in solvents. The temperature-dependent misci-
bility of CF3C6F11 with toluene allowed the hydrosilation of 2-cyclohexen-1-one
with PhMe2SiH at RT under biphasic conditions, with 90–85% distilled yields and
high retention of TON (turnover number) over three cycles using the same charge of
catalyst [RhCl{P(CH2CH2(CF2)n1CF3)3}3] (n ¼ 6, 8).44 Similar results were ob-
tained in one-phase higher temperature reactions with hexane or diethyl ether,
where the catalyst was separated by cooling to 30 1C, when the mixtures phase
separate. The one-phase reactions were faster. Further optimizations were done
with hydrosilation of cyclohexanone. In another report, improved activity of the
fluorous Rh catalysts, making them comparable to RhCl(PPh3)3, is achieved via the
use of 4-silylaryl phosphines that are substituted with fluoroalkyl groups on sil-
icon.45 With a clever reverse approach, recovery and reuse of the non-fluorous
Wilkinson’s catalyst was demonstrated for the hydrosilation of 1H,1H,2H-
perfluoro-1-alkenes, using a fluorinated solvent to extract the product. In yet an-
other novel approach van Koten’s group communicates the use of a fluorous
(imidazolium) ionic liquid to separate a fluorinated version of Wilkinson’s catalyst
that could be recycled up to 15 times without significant loss of activity.46 Although
tungsten is not a member of the Co-triad, a tungsten catalyst was found to pre-
cipitate out via an unusual ‘‘liquid clathrate’’ formation mechanism, following the
consumption of reactants in the hydrosilation of carbonyl compounds (in a solvent-
free medium.)47 Using phase separation of a mixture of solvents that is homoge-
neous at hydrosilation temperature, to separate the catalyst for recycle has also
10 A.K. ROY

been claimed for dried H2PtCl6.48 In the author’s laboratory, indications were
obtained that a certain true Pt catalyst precipitated out at the end of hydrosilation
due to high crystallinity and insolubility in the product, but was capable of re-
dissolving under reaction conditions to catalyze a second charge of reactants with-
out loss of activity and selectivity (see Section IV for catalyst description). Although
the precipitated catalyst was not filtered out, the same behavior was noted for a
different olefinic substrate and silane combination.49
Most new Ir catalysts that have been studied in the last 15 years for hydrosilation
appear to be cationic species. However, Tanke and Crabtree reported a class of
neutral Ir(I) complexes 7 with a very unusual ligand – tris(diphenyloxophosphor-
anyl)methanide, abbreviated as ‘‘triso.’’50 Complexes 7 with cyclooctene (COE or
coe) or ethylene as the ancillary ligand were found to catalyze only terminal alkyne
hydrosilation, with very high Z:E stereoselectivity and b-regiospecificity. Turnover
rate and Z:E ratio were found to be dependent on the steric and electronic character
of the substrate 1-alkyne. In the presence of iminophosphines of the type 2-
Ph2PC6H4NQCR1R2, [IrCl(COD)]2 has been shown to be a moderately active
catalyst for the hydrosilation of acetophenone with Ph2SiH2.51

Ph Ph
P O L
Ph2P Ir
O P O L
Ph Ph

7
L = coe/C2H4/cod/CO

The cationic complexes [Ir(Z2-iPr2PCH2CH2NMe2)(diolefin)][BF4] and [Ir(Z2-

i
Pr2PCH2CH2OMe)(diolefin)][BF4], where diolefin is either 1,5-cyclooctadiene
(COD or cod)) or tetrafluorobenzobarrelene (TFB), efficiently catalyze the hydros-
ilation of phenylacetylene with triethylsilane, although all possible isomeric
products as well as styrene and PhCRCSiEt3 are formed.52 Oro, Sola and
coworkers have reported on the versatility of 1,5-cyclooctadiene as a ligand,
via flexible hapticity, in phenylacetylene hydrosilation catalysis by the cationic
complex [Ir(NCCH3)(PMe3)(Z-1,2,5,6-cod)]BF4.53 The cationic silyl and silylene
complexes [Cp*Ir(H)(PMe3)(Z2-SiPh2C6H4)][B(C6F5)4] and [Cp*Ir(H)(PMe3)
(SiPh2)][B(C6F5)4] have been shown by Tilley, Bergman and Klei to be effective
precatalysts for the hydrosilation of acetophenone with Ph3SiH and Ph2SiH2,
respectively.54 For these complexes, high ability of the anion to dissociate is critical
to catalytic activity, as complexes with triflate anion showed no catalytic behavior.
Finally, the certainty that well-designed, newer ligands will advance the boundaries
of hydrosilation catalysis is beautifully demonstrated by a tandem hydroamination-
hydrosilation reaction communicated by Messerle and coworkers.55 Cationic Ir(I)
complexes 8 and 9, based on bis(pyrazolyl)- and bis(imidazolyl)methane ligands
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 11

catalyze the conversion of 4-pentyne-1-amine to N-silyl-2-methylpyrrolidine, in a

one-pot reaction and in nearly quantitative yields [Eq. (9)]. The internal hydroami-
nation occurs first, but the silane can be added later or may be present in the
starting reaction mixture – a remarkable feature of the two-step reaction.

BPh4 H3C BPh4

N
N N CO N CO
Ir Ir
CO N CO
N N
N
H3C

8 9

C CH [Ir], 8 or 9 [Ir], 8 or 9
C
60 ° C N CH3 Et SiH,60°C N CH3 (9)
NH2 3
SiEt3

IV
NICKEL-TRIAD CATALYSTS
Like its other first-row preceding neighbors, Ni is known to be a rather poor
hydrosilation-catalyst source-metal. Nevertheless, research effort in recent years has
led to the development of Ni-based catalysts that show improved activity, and in
some cases opposite regioselectivity compared to workhorse catalysts based on Pt
or Rh. Of particular note is a series of catalysts 10a–c where an indenyl ligand
anchors the Ni.56 Zargarian and coworkers systematically investigated the effect of
a ring-tethered NMe2 ligand on the activity of the Ni center containing various
phosphine ligands, towards hydrosilation of styrene with PhSiH3 and Ph2SiH2. The
modulating action of the captive, nearby NMe2 ligand on the cationic precatalyst
center generated from 10a was evident from the result that the catalyst species with
PMe3 ligand was the most active, via the balance struck between phosphine donor
strength and steric bulk, when compared with PPh3 and PCy3.56a Yet, the same
research group showed that for precatalyst 10b with a ring substituent incapable of
coordinating to the Ni center, the species containing a PPh3 ligand is a more active
catalyst than one with a PMe3 ligand.56b In the latter case, although the silane/
styrene ratio plays an important role, the ease of dissociation of the phosphine from
the Ni center influences the activity of the catalyst. This is even more accentuated in
10c; the rate of reaction is significantly increased even without cationic initiation
when two Me3Si are present at the 1,3-positions of the ring anchor.56c It is also
noteworthy that all of these catalysts yield the internally or a-silylated product
12 A.K. ROY

almost exclusively, with yields reaching up to 95% when excess PhSiH3 is used
relative to styrene.

Me
R SiMe3
Ni Ni
R 3P Cl Ni
NMe2 R 3P Cl
Ph3P Cl
10a 10b 10c
R = Me,Cy,Ph R = Me,Ph R = H,SiMe3

The use of Ni(0) catalysts for the hydrosilation of phenyl acetylene with Ph3SiH
and of various internal alkynes and conjugated diynes with Ph2SiH2, PhMe2SiH
and Et3SiH has also been reported.57,58 It is of interest to note that although the Ni
equivalent of Karstedt’s catalyst has been prepared, dehydrogenative silylation of
alkenes leading to unsaturated products is the dominant reaction and hydrosilation
a secondary pathway with this Ni catalyst.59
The fact that Pd-based catalysts are not used in industrial hydrosilation processes
(with perhaps rare exceptions), despite their significant commercial utility in the
closely related hydrogenation and in myriad other organic transformations, is the
result of generally low activity of palladium complexes in catalyzing olefin hydros-
ilations in particular. However, Pd compounds often provide selectivity that is
different from that of Pt complexes. For example, Gulinski and James have re-
ported high a-selectivity and a-specificity in the hydrosilations of styrene and vi-
nyltrichlorosilane, respectively, with HSiCl3, using various Pd complexes with
bis(diphenylphospino)methane as a ligand.60 On the other hand, a catalyst based on
Pd2(dba)3  CHCl3 and two moles Cy3P (per mol Pd) provided high yield (0.5 mol%
Pd based on silane), exclusive E-selectivity and very high b:a selectivity for room
temperature hydrosilations of a variety of terminal alkynes with Ph3SiH or Ph2Me-
SiH.61 An unusual rate enhancement was observed by the same research group for
1-octyne hydrosilation when water was used as a solvent.
The ability of Pd complexes to catalyze tandem cyclization–hydrosilation reac-
tions, that could provide a synthetic route to carbocycles of interest in the fields of
biochemistry and medicine, was recently demonstrated. Widenhoefer’s group has
developed phenanthroline-based complexes 11 and others that quite efficiently
bring about this dual transformation for a wide variety of functionalized dienes,
with high regio- and stereoselectivities [e.g., Eq. (10)].62

E [Pd], HSiMe2Ph E SiMe2Ph

E 25°C E
Me (10)
E = CO2Me Single diastereomer, 91%
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 13

N Me
[Pd] = Pd + NaBAr4 Ar = 3,5-bis(trifluoromethyl)phenyl
N Cl

11

There have been a number of important advances in hydrosilation with platinum

compounds and complexes as catalysts. Perhaps the most intriguing of these, for a
rather simple compound of Pt, is that PtO2 has been shown to facilitate hydros-
ilation of unsaturated amines with exceptional selectivity.63 A number of primary,
secondary and even tertiary allylic amines were hydrosilated with methyldiethoxysi-
lane, providing g/b ratios of 95/5 for the corresponding products in total yields
495% (although, distilled yield for 3-aminopropylmethyldimethoxysilane was only
60%). The question remains whether PtO2 leads to an active homogeneous catalyst,
especially since it is claimed to be filterable (no recyclability shown) at the end of
reaction, and Pt/C (10% w/w Pt) yielded identical results. Nevertheless, the
reported results are important from the perspective that allylic amines, whose
hydrosilation is known to be problematic, are important substrates for the man-
ufacture of a number of commercially useful functional silanes and silicones.
Amongst catalyst modifications that achieve purely rate effects, two reports
are noteworthy. One is the hydrosilation rate enhancement in the presence of b-
cyclodextrins, for Karstedt’s catalyst [Pt2(sym-tetramethyldivinyldisiloxane)3]
and Lamoreaux’s catalyst.64 Lamoreaux’s catalyst (prepared from H2PtCl6 and
1-octanol), showed the most dramatic rate accelerations. The second instance
of rate moderation is reported by Endo and collaborators.65 They report the use of
isocyanides in just 2:1 molar ratio with Pt, to dramatically suppress hydrosilation of
vinylsilane (with Et3SiH) or vinyl-terminated siloxane with methylhydrogensiloxane
copolymer until 60–70 1C. Above this temperature, rapid hydrosilation occurs. This
is in contrast with traditional cure inhibitors where a large excess of inhibitor
(relative to Pt), typically alkynols or maleates, is needed to prevent premature cure.
An unusual bicyclic aminophosphine (proazaphosphatrane) ligand, appears to
form a mononuclear Pt complex upon reaction of the bulky phosphine with a
xylene solution of Karstedt’s catalyst. Of several active members of a series of these
catalysts systems, [Pt{P(iBuNCH2CH2)3N}{Z4-(CH2QCHMe2Si)2O}] 12 catalyzes
hydrosilations of a variety of terminal alkynes (including ones containing hetero-
atom functionality) with Ph3SiH or Et3SiH, in a manner exhibiting high stereo- and
regioselectivity. Thus, propargyl alcohol with triphenylsilane yielded a b(E):a
product distribution of 98:2, with no b(Z) product evident [Eq. (11)]. Comparisons
with Karstedt’s catalyst alone showed significant to dramatic improvements for the
14 A.K. ROY

phosphine-based system in most cases. For a similar, phosphine-modified

Karstedt’s catalyst, tandem Pt-catalyzed hydrosilation/Pd-catalyzed cross-coupling
of terminal alkynes has also been reported.66 Recently, the facilitating effect of a
thioether group at the homoallylic position of olefins was demonstrated for
H2PtCl6-catalyzed hydrosilations with PhMe2SiH.67

(11)

Over the last 8 or 9 years a series of papers have been published on platinum
catalysts bearing electron-deficient olefins as activity modifier ligands.68–71 Amongst
several such catalysts derived by modifying Karstedt’s complex, Osborn, Fisher and
coworkers showed the 2-methylnaphthoquinone-ligated complex 13 to be the most
active (compared to Karstedt’s complex alone) and stable, particularly in the pres-
ence of excess 2-methylnaphthoquinone, for the model hydrosilation of trim-
ethylvinylsilane with triethylsilane. Elsevier and collaborators also found various
fumarate complexes 14 (among other similar complexes with maleate and quinones)
to be more active and more stable compared to Pt(norbornene)3 in the hydrosilat-
ion of styrene with triethylsilane. Using an interesting dinuclear complex with
bridging Z2,Z2-olefin-bonded benzoquinone, [Pt(m-benzoquinone)(norbornene)]2 15,
a 92% yield of the b-hydrosilation product was obtained by Itoh, Yamamoto and
Ohno for the hydrosilation of styrene with PhMe2SiH [Eq. (12)].
RO
O
O Pt
Me2Si
O
O Pt OR
Me2Si
O 14
R = H, Me, 2-butyl, phenyl,
13 1-naphthyl, 2-naphthyl

cat. 15 PhMe2Si
CH2=CH-R + PhMe2SiH R
hexane (12)
30 °C,1hour R = phenyl, 92%; R = n-hexyl, 96%
N-heterocyclic-carbene complexes of Pt have also arrived on the scene of hy-
drosilation catalysis. Markó and collaborators report a catalyst where the bridging
siloxane ligand has been replaced with an imidazolylidene ligand to provide a
monomeric complex 16.72 These Pt–carbene catalysts, especially the cyclohexyl-
substituted complex, are much superior to Karstedt’s catalyst for olefin hydros-
ilation with respect to chemo- and regioselectivity, showing a high level of tolerance
for various functional groups containing oxygen and providing good to excellent
yields of product. That Pt–carbene complexes, as a new class of Pt-compounds,
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 15

bring promise for improving various facets of hydrosilation catalysis is further

borne out by Elsevier and coworkers’ account of improved reactions with catalysts
17a, 17b and 18.73 For the hydrosilation of styrene with Et3SiH, 17b and 18 showed
high activity, and although b/a selectivity was about 4/1, almost no dehydrogena-
tive silation product formed.
R' R'
R R R
Me2Si N N R' N
R'
Pt Pt Pt
O R' R'
N N N
Me2Si
R R' R R' R

16 17a 17b
R = Me, cyclohexyl(cy), tBu R = mesityl, R' = CO2Me R = mesityl, R' = CO2Me

Methylenecyclopropanes are useful and highly reactive intermediates in organic

synthesis. Osakada and coworkers have reported the hydrosilation of methylene-
cyclopropanes with a variety of hydrosilanes using PtI2(PPh3)2, Pt(H)I(PPh3)2 or
Pt(H)Cl(PPh3)2 as catalyst, where the ring is preserved in the product and yields are
high in many cases.74 Hydrosilation of enynes, where the stereochemistry and na-
ture of the product are controlled by the geometry (cis or trans) around the olefinic
bond of the substrate as well as by the catalyst (Pt, Rh or Ru), has been described
by Ozawa and coworkers.75
A series of simple alkene–Pt–silyl complexes that are the first true catalyst species
ever to be observed in Pt-catalyzed hydrosilation was recently identified by Roy and
Taylor.76 Of these, 19a was isolated and characterized by multinuclear NMR spec-
troscopy and X-ray crystal structure determination. Although the focused aim of
the project was to elucidate the catalytic cycle with Pt catalysts (as discussed in more
detail in Section X), 19a as well as other members of the series were proven highly
active, stable and recyclable catalysts in the hydrosilation of 1-hexene and styrene
with chlorohydridosilanes.

SiMeCl2
Pt
SiMeCl2

19a
Although their work does not strictly fall within the scope of this review, Hartwig
and Tsukuda’s report on dehydrogenative silation via arene-H and alkane-H
16 A.K. ROY

activation deserves special mention.77 They used a special class of Pt complexes,

[Pt(Me2)(H)(TpMe Me
2 )]{Tp2 ¼ hydridotris(3,5-dimethylpyrazolyl)borate} to demon-
strate inter- or intramolecular C–H and Si–H irreversible dehydrogenative coupling
without the need for a hydrogen acceptor. This new catalytic reaction certainly
blazes a promising path in Si–C bond-forming chemistry.

V
GROUP IVB, GROUP IIIB, LANTHANIDES AND ACTINIDES

As oxophiles, Group IVB transition metals (Ti, Zr and Hf) are perhaps better
suited for the hydrosilation of the CQO unsaturation (which will be addressed in
greater detail in Section VII). Nevertheless, catalysis of SiH addition to car-
bon–carbon and carbon–nitrogen unsaturated compounds have also been investi-
gated to a significant extent, using primarily metallocene complexes. During the
course of their investigation of catalyzed silane oligomerization, Corey and Zhu
discovered that using the catalyst system Cp2MCl2/n-BuLi (MQTi, Zr, Hf), both
acyclic (terminal and internal) and cyclic olefins undergo hydrosilation with
PhMeSiH2.78 The major course of the reaction and the nature of the silated product
are dependent, however, on the type of olefin and the metal. Waymouth and Kesti
studied the hydrosilation of styrene (in detail), as well as that of other olefins with
several silanes (primary, secondary and tertiary), using the active species derived
from [Cp2ZrCl2/2 n-BuLi].79 Only b-silyl adducts were obtained, although styrene
yielded a dehydrogenative silation product as well as ethylbenzene, and product
distribution was dependent on reagent ratios. It was also found that the Zr-based
catalyst gave higher yields of hydrosilation product than similar systems derived
from Ti and Hf. Very recently, however, in a dramatic demonstration of the effect
of changes in catalyst composition, Takahashi et al., showed that when three
equivalents of n-BuLi (instead of 2) per Cp2ZrCl2 are used, the regioselectivity of
the hydrosilation of styrene with Ph2SiH2 is reversed, and only the a- or internal
adduct is obtained.80 This reversal of selectivity with increase in RLi/Zr ratio was
also observed for s-BuLi, but PhLi gave only the a-adduct.
Takahashi’s group has also reported hydrosilation of a number of alkynes with
various silanes, using the [Cp2TiCl2/2 n-BuLi] combination, which leads to products
with excellent regio- and E-selectivity [Eq. (13)].81 It is of note that known zircon-
ocene and hafnocene species do not catalyze the hydrosilation of alkynes.

R2
Cp2TiCl2/2 n-BuLi R1
R1 R2 + H-[Si] [Si]
THF, 1 h
52-97% (13)
R1 = Et, n-Pr, n-Bu, n-pentyl, n-hexyl, n-octyl, SiMe3
R2 = H, Me, Et, n-Pr. [Si] = SiHPh2, SiHMePh, SiH2Ph
Not all combinations of R1 and R2 examined
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 17

Recently, some new alkylzirconium complexes, [Zr(R){N(Ar)SiMe2}3CH]

(RQn-Bu, CH2Ph; ArQp-tolyl, p-fluorophenyl), based on a a tripodal (triamido)
ligand, were found to catalyze alkene hydrosilation, although their catalytic activity
is very poor.82
Harrod, Samuel and coworkers reported selective CQN hydrosilation (with
concomitant partial hydrogenation in most cases) of the aromatic pyridine
ring with PhMeSiH2, using [Cp2TiMe2] as catalyst [Eq. (14)].83 A catalytic
cycle for the reaction is proposed, with [Cp2TiH] envisioned as a key reactive
intermediate in the catalytic cycle. Cp2TiMe2 also catalyzes the reduction of
ethyl benzoate with PhMeSiH2, as well as an interesting reduction-polymerization
of both b- and g-butyrolactone that leads to the alternating copolymers
-[OSiPhMeO(CH2)3CHMe]n- and -[OSiPhMeO(CH2)3CH2]n-, respectively.84 The
highly reactive [Cp2TiH] is also implicated as the ‘‘catalytic’’ species for the reduc-
tion-polymerization reaction.

[Cp2TiMe2],
10 mol%
+ 2 PhMeSiH2 + 1/n(PhMeSi)n
80 °C, 8 h
N N (14)
SiHMePh
94%

It is appropriate to consider Group IIIB, lanthanide and actinide metals together

because of the preponderance of the +3 oxidation state in catalysts based on these
metals. Like Group IVB metal complexes, those of Group IIIB and lanthanide
metals are marked by characteristic Lewis acidic behavior. This is turn has mech-
anistic implications in hydrosilation, particularly with regard to potential olefin
polymerization as a side reaction. Again, as with Group IVB metals, for Group IIIB
and lanthanide/actinide metallocene-based complexes dominate the catalyst scene.
Following discovery efforts by Voskoboynikov,85 Tanaka86 and their coworkers,
the research groups of Marks and of Molander carried out some impressive catalyst
development work in the area, and seminal publications from these groups have
contributed enormously to catalyst refinement and understanding of modus ope-
randi for catalysts based on this group of metals. (For a review of lanthanide
catalysis in organic synthesis, and for additional references of lanthanide catalyzed
hydrosilation, see Ref. [87].) A selected few works of the latter groups, along with
others’ are discussed below.
Of the Group IIIB metals, yttrium and lutetium based catalysts have been
investigated in hydrosilation. Molander and Julius reported [Y(Z5-C5Me5)2{CH(-
SiMe3)2}] to be a selective and efficient precatalyst for hydrosilating mono- and 1,1-
disubstituted olefins.88 Appreciable selectivity and high to excellent yields are
obtained at ambient temperatures with 3 mol% catalyst that take advantage of the
catalyst’s sensitivity to steric effects. For example, 3-vinylcyclohexene is hydrosi-
lated by PhSiH3 only at the exocyclic olefinic bond with 97% isolated yield of the
b- or terminal adduct. For hydrosilation of alkynylsilanes, prepared to probe
hydrosilation of terminal alkynes, which as unprotected substrates are too acidic for
18 A.K. ROY

successful catalyzed reaction, Molander and coworkers clearly demonstrated the

effect of catalyst structure and alkynylsilyl substituent on the substrate.89 However,
regioselectivity control is dominated by catalyst structure (e.g., 20, 21 or 22) where
selectivity improvements are achieved by reducing Cp-substitution or by changing
the metal used. It is noteworthy that one regio- and stereo-isomer is the major
product [Eq. (15)]. Additionally, Molander and Retsch reported hydrosilation of a
variety of internal alkynes (linear, branched and hetero-atom substituted) with
PhSiH3, using [Y(Cp0 2)(Me)(THF)] as precatalyst, where many alkynes afforded a
single product with exclusive (E)-stereochemistry and addition of Si to the less
hindered carbon.90
TMS TMS

Me Me
Y Ln Ln
THF Me

TMS TMS
20 Ln = Y, 21; Ln = Lu, 22; TMS = Me3Si

cat. 20, 21 or 22 H SiH2Ph

n-Octyl [Si]
PhSiH3 n-Octyl [Si] (15)
i t
[Si] = SiMe2H, Si Pr2H, Si Bu2H, SiPh2H, SiMe3 major product

In 1995, Marks and coworkers published a particularly insightful study on the

hydrosilation of aralkenes, 1-alkenes and 1,1-disubstituted alkenes with PhSiH3,
using a number of lanthanide catalysts, but focusing on a series of Sm catalysts
(e.g., 23) with varied ligand structures. The work revealed that alleviation of steric
congestion around the metal’s coordination sphere, either via tying the Cp rings of
the catalyst with a silicon bridge (which creates a cone effect, and blocks one side
but widens the opposite side of the metal to ligand access) or by using a larger ionic
radius metal center, significantly improves both activity and regioselectivity of the
catalyst.91 This is most dramatically demonstrated in the hydrosilation of styrene
with PhSiH3 [Eq. (16)]. Soon thereafter, the ability to use primary silanes as highly
efficient chain terminators for olefin polymerization catalyzed by Y, Lu, La and Sm
metallocene–hydride complexes was demonstrated by Marks’ group.92

H
SiMe3
Me2Si SmC
SiMe3

23
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 19

H
H Cp'2LnR or
+ PhSiH3 SiH2Ph
Me2SiCp"2SmR(23), 60 °C
(16)
Cp' = η 5-Me5C5, Cp" = η5-Me4C5 α- or internal adduct (yield)
Ln = Lu, 5.8 (5.5); Sm, 82 (78);
R = CH(SiMe3)2
Nd, 90 (84); La, 96 (88)
Cp"2Sm, >99 (98)

Hydrosilation of dienes using 1 mol% [Nd(Cp0 2){CH(SiMe3)2}] has been de-

scribed by Tanaka et al.93 With PhSiH3, isoprene yields (E)-2-methyl-2-butenyl-
phenylsilane as the major product, whereas 1,5-hexadiene and 1,6-heptadiene yield
a cyclopentylmethylsilane as the primary product.
In the context of the role of monomer–dimer equilibrium in catalytic activity,
Voskoboynikov et al. have shown that dissociation of a dimeric Ln-precatalyst to a
monomeric species is not an absolute prerequisite for catalytic activity, as hydros-
ilation of 1-octene (to yield primarily the terminal adduct) with PhMeSiH2 dis-
played identical selectivity, rate law and rate constant for a metal whether the dimer
was [LnCp*2(m-H)]2 or [LnCp*2(m-H)(m-Me)]2.94 A dimeric complex, [Y(m-H)(Z5:Z1-
C5Me4CH2SiMe2NCMe3(THF)]2, with a two-atom bridge (CH2SiMe2) between the
Cp ring and the ligating N-atom, was shown to be a more active catalyst than the
one with just a SiMe2 bridge, for the hydrosilation of 1-decene with PhSiH3.95
However, for styrene hydrosilation, this catalyst showed lower selectivity for in-
ternal adduct than achievable with the ‘‘constrained geometry’’ catalyst of
Marks described above. Recently, the first constrained-geometry cyclopentadienyl-
phosphido complexes of the type [Ln(R)(Z5:Z1-C5Me4SiMe2PR0 ] (LnQY, Yb, Lu;
R0 QPh, Cy, 2,4,6-tBu-C6H2-; RQH, CH2SiMe3) in dimeric and other structural
variations, were reported.96 Nearly all the complexes were active towards highly b-
selective hydrosilation of 1-decene with PhSiH3 (rt, 5 mol% Ln), with the ‘‘CyP-
LuCH2SiMe3’’ complex being the most active (100% yield in 10 min). This Lu
complex was also highly active for other olefin hydrosilations.
Once in a while, as was related in the section on Pt catalysts (PtO2), simple and
readily available metal compounds and complexes turn out to be excellent catalysts.
This is also the case with easily obtained La[N(SiMe3)2]3. Livinghouse and Horino97
recently described hydrosilation of a variety of olefins and dienes with PhSiH3 using
the tris-amido compound [Eq. (17)], where high activity and selectivity (at 3 mol%
catalyst, 25 1C) nearly mirror those observed by Marks and coworkers with their
metallocene-based Ln complexes. Yet, the analogous tris-amido complexes of Nd
and Sm exhibited much lower activity, and several other simple lanthanum com-
pounds as well as Y[N(SiMe3)2]3 totally failed to catalyze the very same hydros-
ilation (that of 1-hexene with PhSiH3)! It is this extraordinary difference between
high activity and no activity amongst closely similar Group IIIB/lanthanide metal
complexes that perhaps differentiates this metal group most from the main stream
hydrosilation catalysts based on Pt and Rh. In a positive sense, the stark differences
in activity are potentially exploitable in multi-step transformations or dormant
catalyst applications.
20 A.K. ROY

SiH2Ph
[La{N(SiMe3)2}3], 3 mol%
R + PhSiH3 R
25 °C, 5-40h (17)
R = n-C4H9, C6H5, 4-(MeO)C6H4, yield : 98-99%,
C6H5(of alpha-methylstyrene) α-adduct: 96-99%

In contrast with lanthanide(III) catalysts, some divalent lanthanide complexes

[Ln(Z2-PhNCPh2(hmpa)n)] and [Ln{N(CHPh2)(Ph)}(NPh2)(hmpa)n)] (LnQYb,
Sm, hmpa ¼ hexamethylphosphoric triamide) show considerably different mediat-
ing activity.98 For example, hydrosilation of styrene with PhSiH3 (10 mol% cat-
alyst, THF, rt) yields b- or terminal adduct as the predominant product, and
dehydrogenative silation occurs with terminal alkynes. Additionally, imines, which
are not amenable to hydrosilation with Ln(III) catalysts, are readily hydrosilated by
the Ln(II) compounds in good yields. Further, both types of Yb catalysts yield a
silacyclopentene derivative as a secondary product from reactions of conjugated
dienes with PhSiH3 (and also with Ph2SiH2 for isoprene). It is of interest to note
that although several other metallocene lanthanide catalysts91,93,96 (but not all88)
produce a silylmethylcyclopentane via hydrosilation of a,o-dienes, incorporation of
silicon to afford a silacycle is typically not observed, except also for the tris-amido
lanthanum complex which generates both cyclic products from 1,5-hexadiene and
PhSiH3.97
Although not particularly attractive from the perspective of general synthetic
utility in hydrosilation, effective use of actinide catalysts for the hydrosilation of
terminal alkynes (not viable with lanthanide catalysts) and alkenes has been dem-
onstrated by Eisen and coworkers. Highly chemo- and regioselective hydrosilation
of terminal alkynes (and enynes) with PhSiH3 (affording b(E) adduct in excellent
yield) is achieved with the ligation-facilitating ansa-Me2SiCp00 2Th(nBu)2, where
large rate increases (up to nearly 1000 fold) are observed over the corresponding
Cp0 -based complex (Cp00 QMe4C5, Cp0 QMe5C5).99 Hydrosilation of alkenes also
occurs with the ansa-catalyst to yield primarily b-adduct, but yields are moderate
and considerable amounts of the corresponding alkanes are produced. The same
group has also reported the use of Cp0 2UMe2 to catalyze hydrosilation of terminal
alkynes, but the reactions are influenced heavily by a number of factors, and mul-
tiple products are formed.100

VI
MANGANESE, RHENIUM AND COPPER

These metals, belonging to groups on either side of the main block of transition
metals (Group VIIIB or 8, 9 and 10) commonly examined in hydrosilation catalysis,
have only been employed very rarely to facilitate hydrosilation. Very few reports
have emerged during the last 15 years on catalysts based on these metals and their
use has generally been connected with special cases of hydrosilation.
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 21

Esters have been considered largely inert to hydrosilation, but in 1995 Cutler and
coworkers showed that acetyl complexes of manganese, [Mn{C(O)CH3}
(CO)4(PPh3)] and [Mn{C(O)CH3}(CO)5], effectively catalyze hydrosilation of es-
ters to successively produce silylacetal (with PhSiH3, Ph2SiH2 or Me2PhSiH) and
then ether (with PhSiH3 or Ph2SiH2 but not Me2PhSiH) in moderate to good yields,
using 1.5–3 mol% catalyst.101 Cutler’s group also reported hydrosilation of ketones
with PhMe2SiH and Ph2SiH2 using [Mn(Y)(CO)4L] (YQCH3, C(O)CH3, Br;
LQPPh3, CO) and compared activity of the phosphine–acetyl–carbonyl complex
in particular with Wilkinson’s catalyst Rh(PPh3)3Cl. In several cases, with acetone,
acetophenone, cyclohexanone and 2-cyclohexenone as substrates, activity of the
Mn-based catalyst was superior to that of the Rh complex.102
The first example of hydrosilation catalyzed by a rhenium complex,
[Re(O)2I(PPh3)2], 24, was recently communicated by Toste et al.,103 and its impli-
cations to new avenues in reduction catalysis by high oxidation state transition-
metal complexes has been explored by Thiel.104 The most intriguing aspect of
this catalysis is that reductions, including hydrosilation, have traditionally been
catalyzed with electron-rich transition metals in their lower oxidation states. Buck-
ing this wisdom and practice, the dioxorhenium(V) complex very effectively
catalyzes the hydrosilation of aldehydes and ketones with tertiaryhydrosilanes
at catalyst loading of around 2 mol% and at 60–70 1C, with yields of 60–95%.
Furthermore, the catalyst is tolerant of several functional groups including cases of
amino- and nitro substituents. Indication of any enantioselectivity, however, was
not reported.

PPh3
O
I Re
O
PPh3
24

The role of copper species in the ‘‘Direct Process’’ for the production of me-
thylchlorosilanes from silicon metal and methyl chloride is widely known in silicon
chemistry, but outside of this crucial yet largely mysterious catalytic role, the use of
copper compounds in organosilicon synthesis is extremely rare. However, in 1993
Boudjouk’s group reported the use of Cu2O as well as several other Cu(I), Cu(II)
compounds or metallic copper, in conjunction with TMEDA for the exclusive,
high-yield (490%), b-hydrosilation of methyl acrylate with Cl3SiH or MeCl2SiH
[Eq. (18)].105 The optimal ratio for Cu/TMEDA/acrylate/silane was 7.0/10/20/30,
with a reflux temperature of 80 1C, but addition of reactants to the Cu-TMEDA at
0 1C. Methyl methacrylate gave much lower yields, and triethylsilane or triethoxysi-
lane failed to react. Despite this limited success, the catalysis represents an impor-
tant step forward in the hydrosilation of acrylates, which had only yielded mixtures
of a- and b-adducts with all previously tested catalysts.
22 A.K. ROY

[Cu], TMEDA
CH2=CH C(O)OR + HSiR'Cl2 R'Cl2SiCH2 CH2 C(O)OR

R = Me, Et; R' = Cl, Me, Ph Exclusive β- or terminal adduct (18)

[Cu] = Cu, Cu(I) and Cu(II)
compounds

In yet another example of the utility of N-heterocyclic carbene ligands, the use of
Cu-NHC complexes (e.g., 25) to catalyze the hydrosilation of hindered and func-
tionalized ketones with Et3SiH was very recently described by Nolan and coworkers
[Eq. (19)].106 Functionalities on the ketone substrate such as halide, ether and
tertiary amine are well tolerated and excellent conversions are achievable using
a number of variations of 25 (pre-synthesized or generated in situ) with different
N-substitution on the ring.
Cl
Cu

N N

25

3 mol% (NHC) CuCl

R1R2C=O + R3SiH R1R2CH OSiR3
Toluene, 80°C (19)
NHC = N-Heterocyclic Carbene 65-99%

VII
CATALYSIS BY ACIDS, BASES, OR FREE RADICALS

The use of Lewis acids as catalysts for the hydrosilation of unsaturated com-
pounds, hydrocarbons in particular, has seen a surge of interest and activity over
the last dozen years. This is a refreshing and bold development since Lewis acids are
also excellent catalysts for polymerization of olefins and acetylenes.
In 1993, Otera and collaborators reported a comparative rate study on the re-
duction of aldehydes and ketones by Et3SiH catalyzed by the Lewis acid Me3SiClO4
and the Brønsted acid HClO4, in acetonitrile containing water.107 Surprisingly, even
in the presence of water, the catalytic reaction of Me3SiClO4 (generated from
Ph3CClO4 and Me3SiH) with the carbonyl compound was faster to afford alcohol
products. Catalysis by the silyl perchlorate was at least two orders of magnitude
faster than that by perchloric acid. Aluminum chloride and EtAlCl2 were found
to be very effective catalysts for the hydrosilation of alkynes and allenes by
Et3SiH.108 While HfCl4 gave low yields, ZrCl4 gave only a trace of product, and
Et2AlCl failed to catalyze the reaction. A key feature of the catalysis is the high
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 23

stereoselectivity in terminal or internal alkyne hydrosilation, leading to cis- or Z-

vinylsilane via trans-addition of the Et3SiH [Eq. (20)]. The order of addition of
catalyst and reagents is critical since, in the absence of silane, the Lewis acidic
catalyst can oligomerize the acetylenic substrate.
R1 SiEt3
1 2 AlCl3 or EtAlCl2
R R + Et3SiH
toluene or n-hexane, H R2
0 °C (20)
1
R = alkyl, aryl; β-(Z)-product,
R2 = mostly H, also alkyl, aryl exclusive or major

The first examples of the hydrosilation of linear and cyclic alkenes with trial-
kylsilanes in the presence of a range of Lewis acid catalysts have been reported by
Jung and coworkers.109 Like the alkyne and allene hydrosilations above, the alkene
reactions are also highly regio- and stereoselective, producing the isomer with silyl
addition to the less hindered carbon in moderate to good yields [Eq. (21)]. For cyclic
substrates, such as 1-methylcyclohexene, only the cis-isomer is obtained. The
activity of the catalysts examined follows the order AlBr34AlCl34HfCl44
EtAlCl24ZrCl44TiCl4. Added trialkylchlorosilanes act as promoters, but may
naturally be generated in situ from the trialkylsilane and trace HCl present in the
catalyst. It must be said, however, that despite the surprising ability to mediate
olefin and alkyne hydrosilation, the extreme reactivity of the Al–halogen bond
coupled with the need to use quite high loadings of catalyst, limit the use of
aluminum halide Lewis acids for broad application in hydrosilation.

R1 R2 AlCl3, 0.2 eqv R1 R2

+ Et3SiH H
H R3 CH2Cl2, -20 ˚C to rt Et3Si R3
(21)
R1, R2 = mostly H;
R3 = alkyl, aryl;
R1, R2, R3 = Me

A familiar and synthetically important Lewis acid compound, B(C6F5)3, that

holds much promise of superiority over chloroaluminum species as a hydrosilation
catalyst was recently very successfully utilized by Gevorgyan’s group to add a
number of alkyl- and arylhydrosilanes to a wide variety of linear and cycloaliphatic
as well as aralkenes.110 The products, with the same regio- and stereoselectivity as
with AlCl3-catalyzed reactions, were obtained in mostly excellent yields, using
5 mol% of the borane [Eq. (22)]. In several instances of identical olefin hydros-
ilation, the borane catalyst provided much higher yields of adduct. In a second
instance of B(C6F5)3-catalyzed hydrosilation under mild conditions and low borane
loading, Rosenberg and collaborators very recently communicated an unusual
reaction of silanes or disilanes with thiobenzophenone leading to new types of silyl
thioether compounds.111
24 A.K. ROY

R1 R2 R1 R2
4
B(C6F5)3, 5 mol%
+ (R )3SiH H
H R3 CH2Cl2, rt (R4)3Si R3
(22)
R1, R2 = H, alkyl; 85-98%
R3 = alkyl, aryl;
R4 = alkyl, Ph

Also very recently, Yamazaki and coworkers reported that regioselectivity in

the hydrosilation of propiolate esters with (Me3Si)3SiH is controlled by both
substituents and the presence or absence of a Lewis acid such as AlCl3, EtAlCl2 or
Et2AlCl.112 Methyl and ethyl esters gave a-adduct with AlCl3, but b-adduct in
the absence of Lewis acid or in the presence of either EtAlCl2 or Et2AlCl. On
the other hand, for the trifluoroethyl ester all the Lewis acids gave a-adduct
exclusively. The difference was explained using competitive free-radical and ionic
mechanisms.
Fluoride-on-alumina promoted hydrosilation of benzaldehyde with Et3SiH,
affording benzyloxytriethylsilane quantitatively was described recently.113 The for-
mation of benzylbenzoate as a byproduct via self-condensation of benzaldehyde, is
totally suppressed in DMF as a solvent, whereas in hexane or THF, it is the major
product formed. Other basic species such as KNH2/Al2O3, MgO or CaO showed
much lower activity compared to KF/Al2O3.
Although efforts in free-radical catalyzed hydrosilation continue at a low level,
no major advance has been reported or any particularly useful synthetic application
developed in recent years and over the last decade. In 1992, Boardman reported
results of hydrosilation of 1-octene with Me2HSiOSiMe3 facilitated by photo-ac-
tivated [Pt(Cp)Me3].114 With as little as 10 ppm Pt, and following an initial UV
irradiation, rapid hydrosilation occurred (TON up to 10,000 per Pt per minute),
with nearly quantitative yield of the b-adduct. Evidence indicated involvement of
heterogeneous colloidal Pt as the active species. Lewis and Salvi studied the photo-
initiated (l4300 nm) hydrosilation of triethylvinylsilane with triethyl silane using
[Pt(acac)2] (acac ¼ acetylacetonate) as the precatalyst.115 No reaction was observed
in the dark, but upon short (10 min) irradiation at 25 1C, ca. 85% conversion of
reactants to Et3SiCH2CH2SiEt3 was obtained. Unlike Boardman’s study, inhibition
studies with mercury and DBCOT (dibenzocyclooctatetraene) indicated a homo-
geneous catalytic species during the fast initial stages of hydrosilation.
Rapid hydrosilation of dimethylvinylsilane with near-UV-activated [Pt(acac)2] has
been reported.116 Poly[(dimethyl)vinylsilane] with Mw ca. 5500 g/mol is the major
product but oligomers and other side-products also form. Active species apparently
remain ‘‘alive’’ for extended periods as molecular weight increase of the initial
product to 12,300 g/mol in 6 months is observed. Brook and coworkers, on the
other hand, report relatively poor hydrosilation–polymerization of diphenylvinylsi-
lane via catalysis with radical generators such as AIBN, benzoyl peroxide and
di-tbutyl peroxide.117 Photo-hydrosilation of 1-octene with pentamethyldisiloxane
and of a vinyl-silicone with a hydro-silicone, using four trimethyl(b-dicarbonyl)
Pt(IV) complexes (OEt, Me, Ph, CF3 groups, respectively on carbonyl carbons) was
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 25

examined by Fouassier and coworkers.118 Sonochemically-assisted hydrosilation

of 2- and 4-substituted cyclohexanones, in the presence of Rh(PPh3)3Cl, has been
described.119

VIII
ASYMMETRIC HYDROSILATION

It could be argued that catalytic asymmetric synthesis is one of the top fields of
research currently in organic chemistry. The impetus for the wide and deep interest
in this field is provided primarily by two fronts: the pressing need in the pharma-
ceutical industry to develop new drugs and the rapidly advancing scientific progress
in establishing structure–function/structure–activity relationships and interrelation-
ships of biologically active molecules. It is not too far from the truth to assert that
together with C–C catenation, actually hand-in-hand with it, chirality of molecules
defines the stuff of life. Because of the availability of a number of relatively simple
methods to remove silyl groups from an organic compound to generate new
derivatives, research in asymmetric hydrosilation has grown steadily in the last
15–20 years. Like hydrogenation, hydrosilation offers the potential to convert a sp2
carbon to a sp3 asymmetric center, and not surprisingly catalyst design in asym-
metric hydrogenation has helped guide the development of catalysts for asymmetric
hydrosilation. Several reviews on the subject have already appeared120 and the
summary below will attempt to capture some of the recent advances in this exciting
area of silicon chemistry.
Asymmetric hydrosilation of olefins can be achieved via either Markovnikov or
anti-Markovnikov addition of SiH depending on the olefin substituents, but
for alkynes a double-hydrosilation is necessary to generate a new chiral center.
Hayashi’s group has been instrumental in the development of catalysts for these two
types of unsaturated compounds. Of particular note is the design and development
of monophosphine (–PPh2) or MOP catalysts which were conceived based on the
now-well-known asymmetric ligand template 1,10 -binaphthyl substituted at the 2
and 20 positions with donor groups 26. A large number of MOPs 27 have been
synthesized121 and Pd complexes of many of these are excellent catalysts for the
regio- and enantioselective hydrosilation of various olefins as well as terminal
alkynes. For terminal olefins, a catalyst prepared from [PdCl(Z3-C3H5)] and
(S)–MeO–MOP at P/Pd:2/1, e.g., affords the trichlorosilyl a-adduct in very high
yields, and the corresponding alcohols obtained via oxidative removal of the silyl
group exhibit enantiomeric excesses of 94–97% [Eq. (23)].122 Conversion of
bicycloalkenes such as norbornene to products in 490% ee was also accomplished
with [Pd]/(R)–MeO–MOP.123 Reaction of conjugated dienes (cyclic and acyclic)
with HSiCl3 produces adducts with 62–91% ee, using a Pd catalyst containing a
MOP modified with 6,60 -binaphthyl substituents that help solubilize the catalyst.124
For 1-aralkenes hydrosilated with HSiCl3 and catalyzed by [Pd]/(R)–MeO–MOP,
product yields and enantiomeric excesses range from 80 to 99% and 71 to 85%,
26 A.K. ROY

respectively. Arylacetylenes undergo sequential double hydrosilation with HSiCl3

that are catalyzed by [PtCl2(Z2-C2H4)2] and a Pd-fluoroMOP, respectively, to opt-
imize yield.125 Although yield of the a-adduct is low, enantioselectivity of the vicinal
diols following oxidative cleavage of C–Si is excellent [Eq. (24)].

X = OMe, OCH2Ph, OPr i,

Et, CN, CH2NMe2, CO2Me,
L X
CO2H, OH, H(R),
L´ PPh2 C6H2-3,5-dimethyl-4-OMe,
C6H2-3,5-dimethyl-4-OMe
with bis(6,6´-noctyl)
substituents on binaphthyl
26 27
L, L´ = donor group

[Pd]-MOP,
0.1mol % or less
R + HSiCl3 * SiCl3 + β-adduct
40 °C R
α -adduct
R = n-Bu, n-hex, n-dec, 66-93% (23)
CH2CH2Ph, cyclo-C6H11
(1) EtOH/Et3N
* OH
(2) H2O2, R
KF/KHCO3
94-97%

(1) HSiCl3, [Pt]-0.01 mol%

(2) HSiCl3, [Pd]/F-MOP (R), 0.3 mol% Ar
Ar H OH
(3) H2O2, KF, KHCO3
HO
Ar = Ph, 4-MeC6H4, 4-ClC6H4,
(24)
(R) 94-98% ee
4-CF3C6H4, 3-NO2C6H4

F-MOP phosphine = {m-(CF3)2C6H3}2P,

X = H (27)

Great latitude in tuning Pd complexes toward achieving phenomenal stereose-

lectivity has been demonstrated via use of a ferrocene-anchored P,N-ligand 28. For
the hydrosilation of norbornene, increasing the bulk of the pyrazole substituents
increases yield and ee significantly, and electron-withdrawing 3,5-bis(trifluorome-
thyl)phenyl groups on the phosphine lead to 499.5% enantiomeric excess of the
exo-norborneol derived via oxidation of the silyl-adduct.126 Substrate electronic
effect on stereoselectivity, using 4-substituted styrenes, showed para-substituent
influences on both ee as well as chiral sense of the product that follow the Hammett
linear free-energy relationship. Palladium complexes containing a bidentate ligand
29 with either a P or As donor and a sulfonamide group (O-donor postulated)
exhibited moderate stereoselectivity control for the hydrosilation of conjugated
cyclic dienes with HSiMeCl2.127
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 27

R2
Me
N
PR12 N
Fe R3 NHSO2Me
EPh2

28
R1 = Ph, 3,5-(CF3)2-C6H3
29
R2 = H, Me
E = P,As
R3 = Me, Ph, 9-Anthryl,
2,4,6-Me3-C6H2, 2,4,6-(OMe)3-C6H2

Wiedenhofer and coworkers have employed optically active bisoxazoline

30–32 and pyridine–oxazoline 33 complexes NN0 PdCl2 for the first asymmetric
cyclization–hydrosilation of dienes, primarily diallylmalonates, with tertiary
silanes.128 Whereas the bisoxazoline complexes achieve moderate yields of sily-
lated and non-silylated cyclic mixtures with high diastereoselectivity and moderate
enantioselectivity, the pyridine–oxazoline complexes afford the silylmethyl-carbo-
cycle in high yield, excellent diastereoselectivity and high enatiomeric execess
[Eq. (25)]. Using a Pd catalyst crafted from phosphoramidite-MOP ligands 34 and
35 Johannsen et al. demonstrated moderate to exceptionally high stereoselective
hydrosilation of aromatic alkenes with HSiCl3 [Eq. (26)].129

O O O
O R R
O O
N N
N N
R R R R N N
30 31 32
R = alkyl, aryl (R, R and S,S forms used)

N N
R(or R)
33

R = alkyl, aryl (R and S forms used)

E HSiEt3, [Pd]-33, 0.3 mol% E SiEt3

E NaBAr4, CH2Cl2, - 45-25 °C E
Me
(25)
Exclusive product
E = CO2R, etc. [Pd] = Pd(COD)MeCl, or preformed complex with 33 used
Ar = 3,5-bis(trifluoromethyl)phenyl
28 A.K. ROY

O R O
P N P N
O R O

34 35
R = Me,iPr

SiCl3
R HSiCl3, [Pd]-35, 0.5 mol% R
Ar Ar *
20-40 °C, 16-140 h
Tamao-Fleming
oxidation
Ar = Cl-, NO2-, CF3-, CH3-substituted (26)
phenyl, phenyl. OH
R
R = mostly H Ar *

74-95% isolated yield of silane,

86-99% ee of alcohol

Employing a number of Pd–MOP complexes, with 3,5-disubstituted aryls on the

phosphorus and H, MeO or CN at the 20 position, Pregosin and coworkers achieved
quantitative yields and up to 92% ee in the hydrosilation of styrene with HSiCl3.130
Pregosin’s group also examined metal–ligand bonding in a number of Pd–MOP
complexes, and the significant variation in bonding modes and the resulting diver-
sity in spatial orientation of these MOP complexes observed led them to conclude
that selection and design of MOP ligands for predictable improvements in enan-
tioselective hydrosilation is not a trivial or even simple task.131 Indeed, many papers
published on novel chiral ligands and their metal complexes that only achieve low
to moderate enantiomeric excesses support this assertion.
Unlike the asymmetric hydrosilation of alkenes and acetylenes where Pd catalysts
seem to dominate activity, for enantioselective hydrosilation of ketones a prepon-
derance of Rh-based catalysts have been used, although a few other metals in-
cluding Pd have been examined and some ligand templates such as binaphthyl are in
common.
Using the (R)-[TiCl2(Z5:Z5-C5Me4SiMe2C5H3-menthyl)]/2-nBuLi catalyst system,
White and coworkers accomplished hydrosilation of acetophenone and substituted
acetophenones with PhSiH3 that afford chiral alcohols (following hydrolysis of
adduct) in moderate enantiomeric excesses.132 The (S)-neomenthyl catalyst gave
very low enantioselectivity. A number of heteroaromatic ketones, containing
nitrogen/oxygen/sulfur heterocycles, have been asymmetrically hydrosilated with
poly(methylhydrosiloxane) using a Cu(I)-hydride complex of the ligands 36 and
37.133 Several such substrates (acetyl pyridines, acetyl furan, acetyl thiazoles and
others) provide high yields and very good to excellent stereoselectivity of the
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 29

corresponding chiral alcohols, in toluene or toluene–THF solvent at 78 to 35 1C

and at 1 mol% catalyst.
R O
Ar Ar Ar
Ar
O
MeO P Ar = R' P
MeO P O P
Ar R Ar
Ar Ar
R = t-Bu, R' = OMe; O
R = Me, R' = H
36 37

A Rh(III) complex 38 assembled from a bis-NHC-functionalized binaphthyl lig-

and was found to provide excellent asymmetric induction for the hydrosilation of
aryl methyl ketones and dialkyl ketones with Ph2SiH2, affording yields and ee’s of
85–96% and 67–98%, respectively [Eq. (27)].134 Aryl substitutions include F, Br,
Me, OMe and CF3. Crabtree and coworkers also reported Rh- and Ir-mono-NHC-
binaphthyl complexes for the hydrosilation of acetophenone with Ph2SiH2, but with
these latter complexes ee is moderate (Ir) or low (Rh), although yields are high.135
Recently, the use of Rh complexes 39 with a novel oxazolyl-NHC ligand for the
enantioselective hydrosilation of both aryl/alkyl ketones and dialkyl ketones with
Ph2SiH2 was reported.136 Amongst four variants, one (39c) proved an excellent
catalyst for the hydrosilation [Eq. (28)].

O
N
N N
N
N IO Ar But
Rh Br
Rh
N IO
N
39
Ar = Ph(a); o-Tol(b);
38 Mes(c); 2,6-iPr2-C6H3(d)

R1 (1) 1.5 equiv Ph2SiH2, 2 mol% 38, R1

O * OH (27)
R2 THF, 15 °C, 24 h. (2) hydrolysis R2

R1 (1) Ph2SiH2, 1 mol% 39c, 1.2 mol% AgBF4, R1

O * OH (28)
R2 CH2Cl2, - 60 °C, 10 h. (2) hydrolysis R2

Rhodium complexes derived from chelating bisphosphines anchored to an asym-

metric, ancillary Cp–Re complex exhibit moderate enantioselectivity in the hydros-
ilation of phenyl/alkyl ketones with Ph2SiH2.137 A trans-chelating, planar–chiral
bisphosphine 40, based on a biferrocenyl motif, forms Rh complexes that are
30 A.K. ROY

highly effective for the enantioselective hydrosilation of phenyl/alkyl or dialkyl

ketones with Ar2SiH2 (ArQPh or 3-F-C6H4). Excellent yields (73–99%) and high
ee (60–92%) are obtained, especially with the bis-Et2P ligand.138 P,N-chelating
ligands 41 built on the TADDOL scaffold, form cationic Rh(I)(COD) complexes
that catalyze hydrosilation of acetophenone and derivatives with good to excellent
enantiomeric excess (up to 93%).139

PEt2 Ar Ar
H
O O
O O
P N
Fe Et2P Fe
O O R2
H R1
Ar Ar
40 41
Ar = Ph, 2-naphthyl
R1/R2 = H/iPr

A number of Rh complexes derived from bis(pyridyl)- silane or methanol were

found to provide low enatioselectivity in the hydrosilation of acetophenone.140
Chiral (R,R) 1,2-diaminocyclohexane-based N,P and P,P ligated Rh complexes also
achieved low enantioselectivity for the hydrosilation of acetophenone.141 Cis-‘‘A-
frame’’ phosphine Rh complexes based on bi-naphthol and resorcinol anchors gave
products from the hydrosilation of acetophenone in moderate yields and low en-
antioselectivity.142 Rh(I) phosphine-(sulfinyl)phosphonium ylide complexes that
bind through the carbon center of the ylide have been examined in acetophenone
hydrosilation, but enantiomeric excesses are rather low even though yields are
moderate to good.143 Some monothio- and dithioureas, with high ligand-to-metal
ratio (up to 10:1) have been investigated in Ir-catalyzed hydrosilation of aceto-
phenone, where yields and enantioselectivities vary from low to moderate.144
Korostylev et al. have reported up to 50% ee for hydrosilation of acetophenone
with Ph2SiH2 using Rh–P,N complexes based on ligands assembled from
phosphites and amino-alcohols.145
A second novel Re(V) complex 42 was employed by Toste and coworkers for the
reduction of a wide range of aromatic, heteroaromatic and a,b-unsaturated N-
phosphinyl imines with either HSiMe2Ph or HSiMePh2.146 Good to high yields and
high to often exceptional (95 to 499%) enantioselectivity were achieved, at room
temperature in CH2Cl2. Again, the Re(V) complex stands out as a high oxidation
state metal catalyst that is insensitive to air and moisture exposure. In another
example of highly enatioselective hydrosilation of aromatic N-phosphinyl imines,
Ar–CQN–P(O)(xylyl)2, Lipshutz and coworkers demonstrated the use of a Cu
catalyst, derived from the ligand 43 and CuCl–NaOMe–3.3tBuOH, to achieve ex-
cellent yields and 94–99.3% ee, for the reductions with sym-tetramethyldisiloxane.147
This group also reported excellent asymmetric induction (91–99% ee) in the 1,4-
hydrosilation of a,b-unsaturated esters with poly(methylhydrosiloxane), using Cu
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 31

catalysts derived from 43 or chiral bisphosphinoferrocenes.148 In a rare example of

Ru-catalyzed asymmetric hydrosilation, Ru(PPh3)(oxazolinylferrocenylphosphine)
complexes have been shown to convert ketoximes to chiral amines in good yields and
high enantioselectivities (up to 89%).149

O OMe
R
O
O O P
N 2
Cl
NC Re O P
N Cl
OPPh3
O O OMe
R

42 2

R = 4-tBu-C6H4 43

It is apparent from the above brief excerpts from enantioselective hydrosilations

of acetophenone alone, that chiral ligand selection for predictable high asymmetric
induction is non-trivial. One of the promising and increasingly successful ap-
proaches to new catalyst development is the adoption of combinatorial methods.
Using this tool, and the analytical technique of ‘‘mass spectrometry enantiomeric
excess determination’’ (MSEED) developed in their group, Finn and coworkers
assembled an initial array of 21 P,N ligands based on various amino alcohols,
phosphite tether group and scaffolds related to BINOL and TADDOL.150 Rh
complexes prepared from these ligands in 2:1 and 4:1 ligand:Rh ratio were then
tested for enantiomeric excess in the hydrosilation of 1-naphthyl methyl ketone,
comparing results against (R)-p-tolyl-BINAP and (S)-PyBOX. Following two fur-
ther iterations with refined ligand sets for other ketone hydrosilations, ligand 44
emerged as the most effective, affording 70–94% ee for five of the seven ketone
substrates tested. The authors conclude that the diol base, amino-alcohol, and the
latter’s N-alkyl bulk and chiral sense are all structural features of the ligand that are
important for overall performance. The coordination of the nitrogen to the Rh
could not be determined with certainty, and either a chloro-complex
[RhCl(44)(COD)] with no N-bonding or a cationic complex [Rh(44)(COD)]Cl,
with chelating P,N was presumed to be the active precatalyst.

Ph Ph
H Ph
O O O
P Me
O O N Me
H
Ph Ph Me

44
32 A.K. ROY

IX
APPLIED ASPECTS – SYNTHESIS OF POLYMERS AND MATERIALS

One of the very first polymer applications to incorporate and benefit from hy-
drosilation is of course silicone rubber. However, this section will not cover the
traditional aspects of using the reaction, as practiced in silicone commerce. Instead,
glimpses are provided of the myriad ways hydrosilation has been used creatively to
develop or advance ‘‘simple’’ linear polymers and more structured or ordered
materials. Because of the nearly explosive growth in this area, only limited and
representative structures are provided, as can be accommodated within the scope of
this review, and surface treatments via hydrosilation are omitted in general, except
for special or unusual cases. The types of polymers and materials synthesized using
hydrosilation can be roughly divided into three or four broad classes: (A) linear
polymers containing primarily silicon and carbon (and sometimes other atoms) in
the backbone – many are s–p ‘‘conjugated’’ systems, (B) linear polymers with
pendent groups that confer particular properties, (C) dendritic/hyperbranched sys-
tems or materials based on scaffolds and (D) siloxane or organic polymers that have
been functionalized or otherwise modified through hydrosilation, and studies on the
hydrosilation aspect of reactions with polymeric reactants.
(A) The coupling of p-conjugation in polyacetylene (and related poly-
phenylenevinylenes) and s-conjugation in polysilanes to produce hybrid
materials with potentially new or superior optical or optoelectronic prop-
erties, and/or to generate efficient ceramic precursors, has been an important
area of research in silicon physics, chemistry and materials science. Interests
have been driven by the advancing electronics industry and by new struc-
tural material needs, with a very broad range of potential applications.
A variety of alkyne and hydrosilane difunctional monomers of the AA/BB
and AB types, differing in substitution, positional isomerism and initial
p-conjugation length have been subjected to hydrosilation–polymerization
using a number of different catalysts.
Barton and coworkers carried out the first hydrosilation polymerization of an
ethynylhydrosilane that led to soluble, well-characterized, low-medium molecular
weight poly(methylphenylsilylenevinylene) as a glassy polymer in 95% yield, using
H2PCl6 in THF as catalyst.151 Poly(dimethylsilylenevinylene) was also prepared
similarly [Eq. (29)]. Interestingly, only terminal (anti-Markovnikov) addition of SiH
was observed for the polymers 45, as supported by NMR data, and it also appears
that the hydrosilation was highly stereoselective towards one isomeric backbone
structure. Flexible fibers drawn from the Ph/Me polymer melt could be UV-cross-
linked and pyrolyzed to yield ceramic fibers.

(29)
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 33

Kim and Shim reported polymerization of o-, m- and p-(dimethylsilyl)phenyl-

acetylene, using H2PtCl6 catalysis, where polymer yields of 69%, 89% and 67%,
respectively, were obtained.152 All three polymers 46a–c exhibited similar
UV–visible absorption profiles with lmax 260–270 nm. Fluorescence emissions were
also observed, with an unusual red-shifted emission for 46a which the authors
attribute to possible charge-transfer interaction between Si and the neighboring
alkene group in each unit. Polymer 46a decomposed almost completely on heating
to 800 1C (possibly via silaindene type cyclization), while 46b and 46c afforded 40%
and 65% char yields. The same authors also polymerized 4,40 -diethynylbiphenyl
with Ph2SiH2 or PhMeSiH2.153 lmax values and UV absorption profiles of the
polymers vs. model monomers were nearly identical, indicating that extension of
conjugation through Si–CHQCH2 s–p interaction is not significant. Ceramic
fibers could be processed from the Ph2Si-based polymers.

SiMe2

SiMe2 SiMe2

n a b
n
46a 46b

SiMe2

SiMe2

a b
n
46c

Excellent stereo- and regio-control in hydrosilation–polymerization with m- or

p-diethynylbenzene and m- or p-bis(dimethylsilyl)benzene have been exercised,
using [RhI(PPh3)3] or [RhI(COD)]2 (COD ¼ cycloocta-1,5-diene) as catalyst.154
Heating reactants and catalyst together yields E-polymers, while pre-reacting cat-
alyst and bis-silane followed by dialkyne addition affords Z-polymers, in both
cases with mostly 495% stereoselectivity and very good to excellent yields. No a-
addition is detectable. As with the similar polymers of Barton and of Shim,
UV–Vis spectroscopic studies showed no evidence of extended s–p conjugation,
and absorption, emission and lmax characteristics were correlated with the various
stereo- and positional isomeric combinations present within the polymer back-
bones. Synthesis of a number of poly(silylene–divinylene)s, containing Me, Ph or
vinyl substituents on silicon, via hydrosilation of m- or p-diethynylbenzene with
secondary silanes, employing Pd2(dba)3/PCy3 (dba ¼ dibenzylideneacetone) as
34 A.K. ROY

catalyst has been reported.155 Because Pd catalysis promotes CRC hydrosilation

selectively in the presence of CQC, polymers containing Si-vinyl groups could be
made. Char yields in the range 56–75% (highest, for Si-vinyl) at 980 1C were
obtained for the polymers which also exhibited expected UV–vis absorption and
emission behavior.
Neckers and coworkers have prepared linear and star polymers containing
silylene–vinylene–phenylene units from p-dimethylsilylphenylacetylene and 1,4-diet-
hynylbenzene or 1,3,5-triethynylbenzene, respectively, via Pt(acac)2-catalyzed pho-
tohydrosilation.156 Pi-conjugation chain lengths were varied via incorporation of
consecutive ethynylbenzene units. For these photoluminescent polymers, it is
mainly the vinylenephenylene segments that serve as the fluorescent chromophore.
Kang, Ko and their coworkers have synthesized a number of linear and star-like
(47) chromophores, based on polyaromatic cores, that are separated by silicon
units.157 The syntheses are based on hydrosilation of di- or triethynylbenzene with
HSiMe2Cl using Karstedt’s complex as the preferred catalyst, followed by reaction
with various aryl lithium compounds. High b(E)-selectivity for the hydrosilation is
reported. Preliminary UV–visible spectroscopic studies of some of the bis-silyl and
the tris-silyl fluorophores are also presented.

Si

S
Si

Si

47

A number of silylene–vinylene–phenylene type polymers containing 1–3 fe-

rrocene moieties per repeat unit have been synthesized by Sheridan’s group via
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 35

hydrosilation of various diynes with 1,10 -bis(dimethylsilyl)ferrocene.158 Either

Karstedt’s complex or RhI(PPh3)3 was used as catalyst. Varying levels of regio-
and stereochemical distribution of the repeat units were obtained (Rh provided
mostly b-(Z) product), and the polymers were generally of relatively low molec-
ular weight. Cyclic voltammetry studies showed single redox waves that are sug-
gestive of no through-chain interaction between neighboring ferrocene units.
Liquid crystalline di- and trisiloxanes 48 exhibiting smectic C phases and fer-
roelectric electro-optic switching have been prepared via hydrosilation of a
ferrocene-containing substrate with a 1-undecylenoxy substituent, using Karstedt’s
catalyst.159

O O

O
Fe
O
O
O
O
O
Si Si O
x
x = 1,2
48

(B) The hydrosilation reaction has been very effectively used to functionalize
both siloxanes and organic molecules to confer properties of the one
species on the other, or simply to modify or tune certain characteristics.
Side-chain and chain-end modification of siloxanes is a powerful synthetic
tool for this purpose. Hydrosilation of methacrylate-based hindered amine
light stabilizers (HALS) with sym-tetramethyldisiloxane or tris(dime-
thylsiloxy)methylsilane, leads to products with two or three light-stabilizer
groups in a single molecule.160 Benzophenone-based UV absorbers have
been attached to polysiloxanes via hydrosilation with poly(methylhydro-co-
dimethylsiloxane), using Cp2PtCl2 as catalyst.161 The polymeric actives 49
showed essentially unchanged absorbance wavelengths and extinction
coefficients when compared with the active small molecules. Sulfonation
of silyl ketene acetal modified siloxanes, prepared via hydrosilation,162
yields water-soluble siloxanes 50.163 Carbohydrate-functional siloxanes
have been prepared via two different approaches using hydrosilation.
In one, acrolein diethyl acetal was hydrosilated with SiH-terminal silo-
xanes, followed by transacetalation with glucose.164 SiH rake polymers
initially yielded soluble materials which were not isolable in pure form.
The second approach employed hydrosilation of p-allyloxy-benzaldehyde
glucose acetal, N-allylgluconamide or 1-allylglucose with terminal
SiH-functional siloxanes.165 The OH groups of glucose were protected
prior to hydrosilation and then deprotected via methanolysis after
hydrosilation.
36 A.K. ROY

O O
Si Si Si
n
O O O
Si Si Si Si
x y
O
CH2(CH2)n O O
SO3Na

OH O
49 50

Liquid crystals are of course of immense importance to the electronics industry.

Side-chain liquid-crystalline siloxanes prepared via hydrosilation of mesogens with
poly(methylhydrosiloxane) [Eq. (30), e.g.], and their phase behavior studies using
DSC, optical microscopy and X-ray diffraction have been reported.166,167

Pt(DCPD)Cl2
DCPD = dicyclopentadiene
O O O O
Si Si Si Si Si Si
Hm m

CH2 CH2 O
O n n

(30)

X = OMe, OBu, CN
X

Fullerene C60 undergoes hydrosilation with several chloro- and alkoxyhydrosi-

lanes.168 The silyl-C60 can then be cohydrolyzed with TEOS to generate a ‘‘homo-
geneous’’ hybrid silica-gel. A variety of isocyanate-functional silanes, cyclosiloxanes
and polysiloxanes have been synthesized via reaction of m-TMI [m-
(CH2QC(Me)–C6H4–C(Me)2NQCQO] with the corresponding SiH components,
using Karstedt’s catalyst and without any detrimental reaction at NQCQO.169
The ‘‘cyclotetrasiloxane–tetraisocyanate’’ was successfully converted to poly-
urethanes via reaction with MPEG. Silicone-urethanes/ureas are extremely interest-
ing materials with potential for a number of commercial applications, and this
alternative to allyl-PEG hydrosilation offers a second approach to synthesizing this
class of silicone-organic hybrids. A unique ladder-like, soluble polysiloxane with
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 37

4,40 -oxybis(benzamidopropyl) rungs and a naphthyl substituent on each silicon has

been synthesized via hydrosilation followed by H-bonding-templated hydrolysis-
condensation of the monomeric bis(diethoxysilane).170
Silicone polyethers (SPE) 51, also known as silicone-copolyols (SCP), which are
readily prepared via hydrosilation [Eq. (31)], form a very important class of co-
polymers in the area of commercial surfactants. Their utility, however, goes beyond
the surface properties as they are also highly suited for ion conduction in polymeric
liquid, gel or solid battery applications. A good number of publications have ap-
peared on this utility, and ionic conductivities approaching 1.0  102 S/cm appear
within reach in the near future.171–174 Even oligoethylenoxysilanes and short-chain
siloxanes show promise for good liquid electrolyte conductance.175 Polysiloxanes
with pendent cyclic carbonate176 and sulfonate groups177 were also reported earlier
for this application.

Excess
Me O Me
(EO)a(PO)b H
Me3Si(OSi)x(OSiMe2)yOSiMe3 Me3Si(OSi)x(OSiMe2)yOSiMe3
[Pt] CH2
H
EO = CH2CH2O, CH2 (31)
PO = CH2CH(Me)O
CH2(EO)a(PO)b H
Dimethicone copolyol (DMC)
or Silicone polyether (SPE)
51

(C) Amongst macromolecular architectures, dendrimers, hyperbranched poly-

mers and high molecular weight species ‘‘grown’’ on scaffolds are materials
from which the scientific and technological communities have great expec-
tations. A number of simple and efficient chemistries of silicon lend them-
selves well toward the synthesis of the above type polymeric systems. Among
these, hydrosilation as a catalyzed addition reaction is a very well-suited
transformational tool at the chemist’s disposal. A review on heteroatom-
containing dendrimers has covered hydrosilation-based materials.178 For
example, carbosilane dendrimers of the type 52 have been prepared via al-
ternating Grignard and hydrosilation reactions, starting with SiCl4. This
method allows great versatility as successive chlorosilanes can be HSiCl3 or
HSiRCl2 and the alkenyl Grignard reagent can be many, containing various
methylene spacer lengths, CH2QCH(CH2)nMgX. Not only carbosilane
but also silane and siloxane dendrimers with up to 7th generation layer
have been prepared using hydrosilation with judicious control over reaction
conditions. Despite the immense potential, however, dendrimer synthesis
is tedious and wide-spectrum commercial manufacture will likely be possi-
ble only with developments of peptide-synthesis-like automated or
semi-automated processes.
38 A.K. ROY

Hyperbranched polymers, which are close cousins of dendrimers, are much more
amenable to synthesis, since they only require an AB2 monomer for ‘‘chain’’
growth. In this area, synthesis of a s–p conjugated polymer from the AB2 monomer
m-(HMe2Si)2–C6H3–CRCH has been reported, using RhCl(PPh3)3/NaI as the
stereo- and regioselective catalyst.179 The SiH-ended polymer was capped with ex-
cess phenylacetylene to generate a stable material. Without capping, air oxidation/
hydrolysis and subsequent crosslinking occurs to produce gels and insoluble films
which emit an intense blue light on excitation at the charge-transfer absorption
wavelength.
R O R
O Si O Si
Si O
R SiO
RO
OR O
R O R O Si Si R
O Si O Si O Si O
Si
Si O O
R SiO R R
RO
O 54
OR
O Si Si R
O Si O
Si R = CH2CH2CH2CH2CH2O OMe(CN),
R O R

53 CH2CH2CH2CH2CH2O N=N CN
 A Review of Recent Progress in Catalyzed Homogeneous Hydrosilation 39

The cubic silsesquioxane unit [RSiO1.5]8 53 (R ¼ organic, inorganic or organo-

metallic substituent) presents a three-dimensional inorganic scaffold that is amena-
ble to a wide variety of materials synthesis. Laine and coworkers have investigated
this arena extensively. Using hydrosilation to form a network structure [e.g.,
Eq. (32)] from [vinyl-(Me2SiO)0 or 1–SiO1.5]8 and [H–(Me2SiO)0 or 1–SiO1.5]8, where
the vinyl or H is attached directly or through a siloxane spacer unit to the cage Si,
variation of the pore structure of the material (0.3 nm diameter – cube interior;
1–50 nm diameter – between cubes) has been studied.180 Silsesquioxanes, bearing
liquid crystalline mesogens181–183 (e.g., 54) and photopolymerizable glycidyl
groups181,182 have been made. Completely nano-homogeneous epoxy nanocompos-
ites are derived from either glycidyl- or cyclohexeneoxide-substituted T8 and
aromatic diamines.184 Thermomechanical properties of these materials have
been studied in detail to understand structure–property relationships. Synthesis of
alcohol-soluble silsequioxanes with amine-terminal groups has been reported.185
Here, a chlorosilane precursor to the silsesquioxane was first prepared via hydros-
ilation using Cp2PtCl2 as catalyst. In general, for hydrosilation directly performed
on silsequioxanes, Karstedt’s complex has been the most commonly employed
catalyst, although Speier’s catalyst and Pd complexes have also been used. The
promise of materials based on silsesquioxanes remains high, but ready availability of
core T8 raw materials such as T8-H in large quantities and at economical cost will
likely determine true commercial application of this unique, yet versatile building
block.
H O H C=C O C=C
O Si O Si O Si O Si
Si O Si O
H SiO C=C SiO C O
HO C C
+ O C O
OH O
O Si Si O Si Si C=C
H O Si O
O Si O Si
Si
H O C=C O C=C
H
Pt, Karstedt's
toluene
(32)

Simplistic representation: only β-addition assumed

(D) The polymer literature is replete with examples of silicone-organic hybrid

macromolecules. Just about every major organic polymer class, from
polyolefins to polyesters to polyimides, has been covalently linked to
Exploring the Variety of Random
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