PART I

FUNDAMENTALS OF SILICON
REACTIVITY: REACTIVE
INTERMEDIATES AND
REACTION MECHANISMS
 ORGANOSILANES: WHERE TO
FIND THEM, WHAT TO CALL
THEM, HOW TO DETECT THEM

1.1. INTRODUCTION

Silicon is the most interesting element in the author’s (unbiased?) opinion.

Silicon does not possess the multitude of stable bonding configurations of
carbon. This makes the probability of discovering a life form based on silicon
somewhat low, in spite of the attractiveness of this concept in science fiction.’
However, silicon forms bonds with most of the other elements of the periodic
table. As a result, it has important inorganic, organic, and polymer chemistries.
Moreover, there is a lot of it on the planet (ca. 28% in the earth’s crust).* As a
result of its ready availability and the special properties that it possesses, the
interest in developing these chemistries and exploiting silicon and silicon-
containing materials continues to increase.
Traditionally, silicon was used in its most common inorganic form, that is, as
silica (see Chapter 10) and silicate rock. The applications using silicon in these
forms continue to be extremely important. For instance, much of the 5.5 billion
tons of concrete poured every year is composed of inorganic silicon (about 20%
silica or about 10% silicon by eight).^ The information age in which we find
ourselves is dependent upon inorganic silicon in a different form; computer chips
are prepared from pure elemental silicon.
The study of organosilicon chemistry is over 100 years old. Organosilanes are
not natural compounds? They were first prepared using the Friedel and Crafts
dialkylzinc r e a ~ t i o nThe
. ~ chemist with the largest early impact on the field was
Frederick Stanley Kipping, who worked in the early part of the twentieth
century. He demonstrated, for example, the generality of Grignard reactions for
the preparation of organosilanes.6 The reading of his manuscripts is truly
enlightening, and much of the work described therein remains surprisingly
relevant to the problems of those currently investigating the field.7 His work has
3
4 ORGANOSIIANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

been recognized through the American Chemical Society Award for Organo-
silicon Chemistry, which bears his name.
An important watershed in organosilicon chemistry was the essentially
+
simultaneous discovery of the Direct Reaction (Si MeCl + Me2SiC12) by
Eugene Rochow and by Richard Muller in 1941-1942 (see Chapter 12).* With
the advent of this process, functional organosilanes became widely available for
the first time, although the variety of available alkylsilanes was initially
somewhat limited. Silane monomers are turned into silicon-based organome-
tallic polymers, silicones, which are high-value products now found ubiquitously
in the developed world: Over lo9kg of silicones are produced each year (see
Chapter 9).' Many current applications rely on the intriguing properties these
materials possess, including high thermal and electrical stability and very low
surface energy, which are much different from organic polymers.
The monomers, from which polymeric organosilanes are made, also possess
unusual properties. As a result, therefore, small organosilanes are increasingly
utilized in a variety of different industrial applications. In the pharmaceutical
industry, for instance, silane protecting groups for organic functional groups are
used both because of the ease of introduction and cleavage of the groups and
because of the relatively low toxicity of the silane species and their byproducts
(see Chapter 8). The ability to use organosilanes to protect sensitive functional
groups has been extended to transition metal ligands and complexes. The
introduction of minerals into organic polymers (e.g., silica fillers in silicones,
fiberglass-reinforced polyesters) requires the organofunctionalization of the
inorganic surface, another type of protective role filled by organosilanes (see
Chapter 10). In addition, the increased volatility of organosilicon-functionalized
main group compounds, when compared to the analogous hydrogen functiona-
lized species, has been exploited by mass spectrometrists to improve sample
introduction" and by those interested in fabricating semiconductors using the
chemical vapor deposition (CVD) process.' ',12 The use of organosilanes to
control carbon-carbon bond formation in organic synthesis is increasingly
exploited and remains an active area of research (see Chapters 8 and 16).
We shall try, in this book, to focus on organosilanes and silicon-based
polymers, the interesting properties of which may be directly attributed to
silicon. We shall further attempt to explain the origins of these properties and to
outline the applications that result from them. To do so, the basic properties of
silicon-containing species in the silicon (see Chapter 2) and organic worlds (see
Chapter 14) will be described, including reactive intermediates based on silicon
(see Chapter 3). This will allow a more detailed discussion of nucleophilic
substitution (see Chapter 5), the most important mechanism for bond formation
at silicon, and the role of extracoordination in that process (see Chapter 4). In the
rest of the book, the preparation and cleavage of non-carbon bonds to silicon
(Chapters 6-1 l), and then of carbon bonds to silicon (Chapters 12-16), will be
discussed. A brief foray into the area of inorganic, organic, and polymeric silicon
as it relates to biological systems is included because the author believes this is
an important frontier for silicon chemists (Chapter 13). As a consequence of
 REFERENCES 5

space limitations, short shrift (or no shrift) will be given to important areas such
as transition metal-based silicon chemistry (see, however, Chapter 6), silicon
photochemistry, silicon rearrangements (see Chapter 15), silicon-based
preceramics, ceramics, and the chemistry of silica (see Chapters 10 and ll),
which at the time of writing is undergoing something of a renaissance.
This book is very much written from the point of view of a synthetic chemist
and focuses primarily on reactions occurring at lower temperatures (< 200”C),
giving products that can be isolated in reasonable yield. It is hoped that, having
read the book, the reader will recognize that the chemistry and properties of
silicon-containing compounds transcend the traditional areas of inorganic,
organic, and polymer chemistry and that there is considerable advantage in
creating and using organosilicon compounds. In the rest of this chapter, we
provide a brief introduction to “what you should know before working with
silicon.” This includes other places to look for information, some simple silane
nomenclature, and NMR data for use in characterizing organosilicon com-
pounds, once you have made them.

1.2. REFERENCES

The author has made an attempt to present relevant references to monographs,

reviews, and original literature throughout the book. Space precludes exhaustive
referencing; inevitably important references will have been omitted. The reader
looking for more detailed background information is referred to the selected
references shown below. These are loosely divided into different chemical
categories. Special note needs to be made of the first reference. The book of
Eaborn stands as a unique source of information. While there have been many
extensions in the field since 1960, his book completely covers organosilicon
chemistry and should be read by those interested in the subject. Similarly, the
overview of silicone chemistry by No11 must be seen as one of the standard
references in the field. Like Eaborn, it has not become dated since the English
version became available in 1968. The most detailed recent overviews of the
field of organosilicon chemistry appear in two volumes edited by Patai,
Rappoport, and Apeloig.

1.2.1. General References

1. Eaborn, C. Organosilicon Compounds, Butterworths: London, 1960.
2. The Chemistry of Organic Silicon Compounds, Wiley: Chichester, UK, Rappoport,
Z.; Apeloig, Y., Eds., 1998, Vol. 2; Patai; S.; Rappoport, Z., Eds., 1989, Vol. 1.
3. Sommer, L. H. Stereochernistry, Mechanism & Silicon, McGraw Hill: New York,
1965.

1.2.2. Organometallic and Inorganic Chemistry

4. (a) Armitage, D. A. Organosilanes, In Comprehensive Organometallic Chemistry II:
A Review of the Literature 1982-1994, Wilkinson, G.; Stone, F. G. A.; Abel, E. W.,
6 ORGANOSILANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

Eds., Davies, A. G., Vol. Ed., Pergamon: Oxford, 1982, Vol. 2, Chap. 1, p. 1.
(b) Armitage, D. A. Organosilanes, In Comprehensive Organometallic Chemistry,
Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds., Pergamon: Oxford, 1995, Vol. 2,
Chap. 9.1, p. 1.
5. (a) Aylett, B. J.; Sullivan, A. C. Carbacyclic Silanes, In Comprehensive Organo-
metallic Chemistry II: A Review of the Literature 1982-1994,Wilkinson, G.; Stone,
F. G. A.; Abel, E. W., Eds., Davies, A. G., Vol. Ed., Pergamon: Oxford, 1982, Vol. 2,
Chap. 2, p. 45. (b) Barton, T. J. Carbocyclic Silanes, In Comprehensive Organo-
metallic Chemistry, Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds., Pergamon:
Oxford, 1982, Vol. 2, Chap. 9.2, p. 205.
6. (a) West, R. Organopolysilanes, In Comprehensive Organometallic Chemistry II: A
Review of the Literature 1982-1994,Wilkinson, G.; Stone, F. G. A.; Abel, E. W.,
Eds., Davies, A. G., Vol. Ed., Pergamon: Oxford, 1982, Vol. 2, Chap. 3, p. 77.
(b) West, R. Organopolysilanes, In Comprehensive Organometallic Chemistry,
Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds., Pergamon: Oxford, 1982,
Vol. 2, Chap. 9.4, p. 365.
7. Many volumes of Adv. Organomet. Chem. have been devoted to silicon-based
reactive intermediates. As an example, Vol. 39 contains reviews on Si=C, Si=N,
Si=P and Si=As, Si=Si, and Si=Ge.
8. J o u m l of Organometallic Chemistry Library Series Volume 1-13, Seyferth, D., Ed.,
Elsevier: New York, 1976-1984.
9. Voronkov, M. G.; Mileshkevitch, V. P.; Yuzhelevskii, Yu. A. The Siloxane Bond,
Consultants Bureau: New York, 1978, translation of Siloksanovaya Svyaz, Nauka:
Novosybirsk, 1976.

1.2.3. Analytical Chemistry

10. Smith, A. L. The Analytical Chemistry of Silicones (Part of Chemical Analysis,
Vol. II2),Wiley: New York, 1991.
11. Bazant, V.; Chvalovsky, V.; Rathousky, J. Organosilicon Compounds ( a compilation
of chemical properties), 1st Serial: Academic: New York, 1965; 2nd Serial: Dekker:
New York, 1973; 3rd Serial: Inst. Chem. Proc. Fundamentals: Prague, 1977; 4th
Serial: Inst. Chem. Proc. Fundamentals: Prague, 1980.
12. Chapters on the History (A), Element and Compounds (B), and Organic Silicon
Compounds (C) may be found in Gmelins Handbuch der Anorganischen Chemie,
Verlag Chemie: Weinheim, 1958, plus several more recent supplements.

1.2.4. Organic Chemistry

13. Weber, W. P. Silicon Reagents in Organic Synthesis, Springer: Berlin, 1983.
14. Colvin, E. W. Silicon in Organic Synthesis, Butterworths: London, 1981.
15. Fleming, I.; Barbero, A.; Walter, D. Stereochemical Control in Organic Synthesis
Using Silicon-Containing Compounds, Chem. Rev. 1997, 97, 2063.
16. Fleming, I. Organic Silicon Compounds, In Comprehensive Organic Chemistry,
Barton, D. H. R.; Ollis, D.; Neville, J. D., Eds., Pergamon: Oxford, 1979, Vol. 3,
Chap. 13, p. 539.
 REFERENCES 7

17. Colvin, E. W. Silicon, In Comprehensive Organometallic Chemistry II: A Review of

the Literature 19824994, Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Eds.,
McKillop, A., Vol. Ed., Pergamon: Oxford, 1982, Vol. 2, Chap. 1, p. 1.
18. Advances in Silicon Chemistry, Larson, G . L., Ed., JAI: Greenwich, CT, 1996, Vol. 3;
1993, Vol. 2; 1991, Vol. 1.
19. Panek, J. S. Silicon Stabilization, In Comprehensive Organic Synthesis, Trost,
B. M.; Fleming, I., Eds., Schreiber, S. L., Vol. Ed., Pergamon: Oxford, 1991,
Vol. 1, Chap. 2.5, p. 579.
20. Fleming, I. Allylsilanes, Allylstannanes and Related Systems, In Comprehensive
Organic Synthesis, Trost, B. M.; Fleming, I., Eds., Schreiber, S. L., Vol. Ed.,
Pergamon: Oxford, 1991, Vol. 2, Chap. 2.2, p. 563.
21. Colvin, E. W. Oxidation of Carbon-Silicon Bonds, In Comprehensive Organic
Synthesis, Trost, B. M.; Fleming, I., Eds., Ley, S. V., Vol. Ed., Pergamon: Oxford,
1991, Vol. 7, Chap. 4.3, p. 641.
22. Marceniec, B.; Gulinski, J.; Urbaniak, W.; Kornetka, Z. W. Comprehensive Hand-
book on Hydrosilylation Chemistry, Pergamon: Oxford, 1992.
23. Hiyama, T.; Kusumoto, T. Hydrosilylation of C=C and CGC, In Comprehensive
Organic Synthesis, Trost, B. M.; Fleming, I., Eds., Fleming I., Vol. Ed., Pergamon:
Oxford, 1991, Vol. 8, Chap. 3.12, p. 763.
24. Magnus, P. D.; Sarkar, T.; Djuric, S. Silicon Compounds in Organic Synthesis, In
Comprehensive Organometallic Chemistry, Wilkinson, G., Ed., Pergamon: Oxford,
1982, Vol. 7, Chap. 48, p. 515.
25. Eaborn, C.; Bott, W. Synthesis and Reaction of the Silicon-Carbon Bond, In
Organometallic Compounds of the Group N Elements, MacDairmid, A. G., Ed.,
Dekker: New York, 1968, Vol. 1, Chap. 2, p. 144.
26. Armitage, D. A. Heterocyclic Rings Containing Silicon, Germanium, Tin or Lead, In
Comprehensive Heterocyclic Chemistry, Katritzky, A. R.; Rees, C. W., Eds., Meth-
Conn, O., Vol. Ed., Pergamon: Oxford, 1984, Vol. 1, Chap. 1.20, p. 573.

1.2.5. Silicone and Polymer Chemistry

27. Noll, W. Chemistry and Technology of Silicones, Academic: New York, 1968.
28. Siloxane Polymers, Clarson, S. J.; Semlyen, J. A., Eds., Prentice Hall: Englewood
Cliffs, NJ, 1993.
29. Silicon in Polymer Synthesis, Kricheldorf, H. R., Ed., Springer: Berlin, 1996.
30. (a) Brown, S. S.; Kendrick, T. C.; McVie, J.; Thomas, D. R. Silicones, In Compre-
hensive Organometallic Chemistry II: A Review of the Literature 1982-1994,
Wilkinson, G.;Stone, F. G. A.; Abel, E. W., Eds., Davies, A. G., Vol. Ed., Pergamon:
Oxford, 1982, Vol. 2, Chap. 4, p. 111. (b) Stark, F. 0.;
Falander, J. R.; Wright, A. P.
Silicones, In Comprehensive Organometallic Chemistry, Wilkinson, G.; Stone, F. G.
A.; Abel, E. W., Eds., Pergamon: Oxford, 1982, Vol. 2, Chap. 34, p. 305.
31. Kendrick, J. C.; Parbhoo, B. M.; White, J. W. Polymerization of Cyclosiloxanes, In
Comprehensive Polymer Science, Allen, G.; Bevington, J. C., Eds., Eastmond, G. C.;
Ledwith, A.; Russo, S.; Sigwalt, P., Vol. Eds., Pergamon: Oxford, 1989, Vol. 4,
Chap. 25, p. 459.
8 ORGANOSIIANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

32. Lebrun, J. J.; Porte, H. Polysiloxanes, In ComprehensivePolymer Science, Allen, G.;

Bevington, J. C., Eds., Eastmond, G. C.; Ledwith, A.; Russo, S.; Sigwalt, P., Vol.
Eds., Pergamon: Oxford, 1989, Vol. 5, Chap. 34, p. 593.

1.2.6. Industrial Applications of Organosilanes and Silicones

33. Chapters on Silica, Vol. 21, p. 977; Silicon, Vol. 21, p. 1084, Silicon Compounds,Vol.
22, p. 1, Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., Kroschwitz,
J. I.; Howe-Grant, M., Eds., Wiley: New York, 1997.
34. Chapters on Silica, Vol. A23, p. 583, Silicates, Vol. A23, p. 661, Silicon, Vol. A23,
p. 721, Silicon Carbide, Vol. A23, p. 746, Inorganic Silicon Compounds, Vol. A24,
p. 1, Organic Silicon Compounds, Vol. A24, p. 21, Silicones, Vol. A24, p. 57,
Ullman’s Encyclopedia of Industrial Chemistry, 5th Ed., Elvers, B.; Hawkins, S.;
Russey, W.; Schulz, G. W., Eds., VCH: Weinheim, 1993.
35. Tomanek, A. Silicones & Industry, Hanser: Munich (published by Wacker-Chemie),
1991.

1.2.7. Silica Chemistry and Silane Coupling Agents

36. Iler, R.K. The chemistry of Silica, Wiley: New York, 1979.
37. Vansant, E. E; Van Der Voort, P.; Vrancken, K. C. Characterizationand Chemical
Modijication of the Silica &$ace, In Studies in Su$ace Science and Catalysis,
Delmon, B.; Yates, J. T., Eds., Vol. 93, Elsevier: Amsterdam, 1995.
38. Plueddemann, E. P. Silane Coupling Agents, 2nd Ed., Plenum: New York, 1991.
39. Silanes, Sulfaces and Intelfaces, Leyden, D. E., Ed., Gordon and Breach Amster-
dam, 1986.

1.2.8. Surface Chemistry of Silicon

40. Waltenburg, H. N.; Yaters, J. T., Jr. Chem. Rev. 1995, 95, 1589.
41. Catalyzed Direct Reactions of Silicon (Studies in Organic Chemistry 49), Lewis,
K. M.; Rethwisch, D. G., Eds., Elsevier: Amsterdam, 1993.

1.2.9. Recent Conference Proceedings and Special Symposia

42. Silicon Chemistry, Michl, J., Ed., Chem. Rev. 1995, 95 (July/August).
43. Silicon-Based Polymer Science (Proceedings of the Silicon Polymer Symposium at
Pacijichem, Hawaii, 1989), Ziegler, J. M.; Fearon, F. W. G., Eds., American
Chemical Society (ACS Symposium Series 224): Washington, 1990.
44. Silicon-Containing Polymers (Proceedings of an RSC Macro Group Symposium,
UniversityofKent, 1994),Jones, R. G., Ed., Royal Society of Chemistry: Cambridge,
1995.
45. Tailor-Made Silicon Oxygen Compounds: From Molecules to Materials (Proceed-
ings of a workshop at University of Bielefeld, G e m n y , 1995), Coniu, R.; Jutzi, P.,
Eds., Braunschweig: Wiesbaden, 1996.
 NOMENCLATURE 9

46. Progress in Organosilicon Chemistry (Proceedings of the 10th International

Symposium on Organosilicon Chemistry, Poznan, Poland, 1993), Marceniec, B.;
Chojnowski, J., Eds., Gordon & Breach: Basel, 1995.
47. Frontiers of Organosilicon Chemistry (Proceedingsof the 9th International Sympo-
sium on OrganosiliconChemistry, Edinburgh, 1990),Bassindale, A. R.; Gaspar, P. P.,
Eds., Royal Society of Chemistry: Cambridge, 1991.
48. Silicon chemistry (Proceedings of the 8th International Symposium on Organosi-
licon Chemistry, St. Louis, 1987),Corey, J . Y.; Corey, E. R.; Gaspar, P., Eds., Ellis
Horwood: Sussex, UK, 1988.
49. Organosilicon Chemistry: From Molecules to Materials III (Proceedings of the
Munich Silicon Days, 1996), Auner, N.; Weiss, J., Eds., Wiley: New York, 1998.
50. Organosilicon Chemistry: From Molecules to Materials II (Proceedings of the
Munich Silicon Days, 1994), Auner, N.; Weiss, J., Eds., VCH: Weinheim, 1996.
5 1. Organosilicon Chemistry: From Molecules to Materials I (Proceedings of the
Munich Silicon Days, 1992), Auner, N.; Weiss, J., Eds., VCH: Weinheim, 1994.
52. Organosilicon and Bioorganosilicon Chemistry (Proceedings of a conference in
Sendai, Japan, 1984), Sakurai, H., Ed., Horwood: Sussex, UK, 1985.
53. (a) Recent Developments in the Use of Silicon in Organic Synthesis, Reich, H., Ed.,
Tetrahedron (Symposium in Print 7 ) 1983, 39(6). (b) Organosilicon Chemistry in
Organic Synthesis, Fleming, I., Ed., Tetrahedron (Symposium in Print 32) 1988,
44(13).

1.2.10. Free References

54. Useful reviews on various aspects of silicon chemistry may be found in the catalogs
of (a) Gelest (Tullytown) and (b) United Chemical Technologies (formerly Petrarch
Systems, Bristol) both of Pennsylvania, USA. For an excellent review on silyl
protecting groups, see: (c) van Look, G.; Simchen, G.; Heberle, J. Silylating Agents,
Fluka: Buchs, Switzerland, 1995 (at the time of writing this was available on request
from Fluka Chemie AG).

1.3. NOMENCLATURE

A detailed summary of silane nomenclature may be found in Eaborn’s b00k.l~

Only the most important silicon-based functional groups will be included here.

1.31. Silanes
As with carbon, much silicon nomenclature is based on the simplest hydrosilane,
silane itself ( S i b ) . The exchange of H for other substituents leads to compounds
that are named as are organic compounds, with alphabetical order taking
precedence. In normal usage, there are many exceptions to these general rules.

H3SiSiH3 disilane
Me2SiC1;? dichlorodimethylsilane (dimethyldichlorosilane)
Ph3SiSiMe3 1,1,l-trimethyl-2,2,2-triphenyldisilane
10 ORGANOSILANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

1.3.2. Sllazanes
Compounds containing silicon-nitrogen bonds take the special name siluzune.
Depending on the number of Si atoms, these compounds are called disilazanes,
trisilazanes, etc.

H3Si-NH-SiH2-NH-SiH3 trisilazane
Note that H3Si-NH-SiH2-NH2 is 1-aminodisilazane.
((H3C)3Si)2NH hexamethyldisilazane

1.3.3. Siloxanes
In a similar vein, silicon-oxygen bonds are known as siloxanes. Polysiloxanes
are silicone polymers (see Section 1.3.7).

H3Si(OSiH2),0SiH3 n = 0, disiloxane
n = 4, hexasiloxane
(H3C)3SiOSiH3 l , l ,1-trimethyldisiloxane

1.3.4. Cyclic Compounds

Cyclic systems are numbered like the carbocyclic systems but named as
cyclopolysilanes. Similarly, cyclic siloxanes and silazanes are named by the
number of silicon atoms, appended functional groups, and the addition of the
prefix cyclo (Chart 1-1). The permethylated cyclosiloxanes are commonly
described using the General Electric nomenclature (D3, etc., see Section 1.3.7).

Mepl
0-Si
H*

hexamethylcyclotrisilane cyclotrisiloxane hexamethylcyclotrisiloxane 2-methoxy-

(D3) cyc~otrisi~oxane’~

Chart 1-1

1.3.5. Substituted Silanes

As in organic nomenclature, there is frequently a choice, for convenience,
between the naming of functional silanes. For instance, Si-OH compounds may
be described as silanols or hydroxysilanes. Some additional considerations in
organosilane nomenclature include (see Table 1.1):
Hulosilunes: The consideration of halosilanes as “salts” is an aberration
of both carbon and silicon nomenclature. However, one will frequently
encounter the incorrect use of “trimethylsilyl chloride” instead of chloro-
trimethylsilane.
 NOMENCLATURE 11

Table 1.1. Nomenclature of Functional Silanes

Structure Silane name

silanol
dimethylsilanediol
t-butylsilanetriol

cyclohexasilanol or
hydroxycyclohexasilane

CH3CH2SiH2SiH3 ethyldisilane
CI3Si-O-SiC13 hexachlorodisiloxane
Bu2SiC12 dibutyldichlorosilane
H3SiNH2 silazane (silylamine)
H2Si(NH2)2 aminosilazane (silanediamine,
diaminosilane)
(CH3)3SiOCOCH3 acetoxytrimethylsilane(trimethylsilyl
acetate)
H3Si-O-SiH2-O-CH2-O-SiH2-O-SiH32,4,6,8-tetraoxa-5-carbanonasilane

octaphenyloxacyclopentasilane
2,2-dichloro-l-trimethylsiloxytrisilane
(l,l,l-trimethyl-3-(1,1-
dichlorodisilany1)disiloxane)

2-bromo-1-chloro-1,l-dimethyl-Zphenyl-

Me3SiOK
0 3-propyltrisilane
potassium trimethylsilanolate

sodium metasilicate

(Na0)Si sodium orthosilicate

PhSi(OMe)4- K+ potassium tetramethoxyphenylsiliconate
Na2SiFs sodium hexafluorosilicate
CH3CH2SiF;- 2K+ dipotassium ethylpentafluorosilicate

Hydrosilunes: Because a hydrogen attached to Si is rather reactive, unlike

the corresponding case with carbon, it is often useful to explicitly refer to a
“hydrosilane” or “organosilicon hydride” for compounds containing the Si-H
functional group. The term “organosilane” does not necessarily indicate the
presence of an Si-H group.
Silunol salts: The analogues to alkoxides are known as silanolates.
Extrucoordinate silicon: Unlike carbon, silicon can easily expand its
coordination shell from 4- to 5- and 6-coordinate (see Chapter 4). The latter
two types of compounds are known as silicates (pentacoordinate compounds
12 ORGANOSILANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

may also be referred to as siliconates). Silicates, of course, are also the salts of
silicic acid The structure of the extracoordinate (5- versus 6-) com-
pounds is obvious from the number of substituents contained in the name. For
pentacoordinate compounds, which typically form trigonal bipyramidal
structures, one must further label the equatorial and axial substituents.
Reuctive Silicon Species: Many of the exciting developments in organosi-
licon chemistry have arisen from the preparation of stable versions of normally
reactive silicon-based intermediates. The nomenclature commonly used for
reactive intermediates may be found in Table 1.2. The prefix “silu” implies a
carbon compound with silicon replacing a carbon, rather than a carbon com-
pound containing a pendant silyl group. For instance, silaethylene (silaethene) is
H2Si=CH2;silylethylene (silylethene) is H3SiHC=CH2.

1.3.6. Organic wersus Organosilicon Nomenclature

The usage of nomenclature for organosilanes is often tempered by the
perspective of the scientist. The subset of scientists who think of themselves
as “silicon chemists” tend to use the silane nomenclature, with the organic
residue demoted to substituent status. On the other hand, organic chemists
typically focus on the organic skeleton and see the silyl group as another
heteroatom-based substituent. The proper nomenclature for silicon-containing
radicals, when appended to an organic structure, is shown in Table 1.3.

1.3.7. Silicones: General Electric Siloxane Notation

The basic building blocks produced by the silicone industry are functional,
methylated silanes that are then hydrolyzed to give siloxanes (see Chapter 9). In
order to facilitate the description of these compounds, the presence of methyl
groups is assumed unless otherwise specified. Silicone components are differen-
tiated by the number of oxygen attachments (M = monofunctional, D =
difunctional, etc.). The combination of these terms allows the facile description
of a complex silicone polymer structure (Chart 1-2). In cases where a methyl

Table 1.2. Nomenclature for Silicon-Based Reactive Intermediates and Relatively

Unstable Compounds

Reactive intermediate Nomenclature

R2Si: silylene (carbene analogue)
R3Si+ silylium ion (silacenium ion, silicon cation)
R3Si’ silyl radical
R$i- silyl anion
R2C=SiR‘2 silene (alkene analogue)
R2Si=SiR; disilene (alkene analogue)
R2Si=0 silanone (ketone analogue)
R2Si=NR ’ silanimine (imine analogue)
 NMR CHARACTERIZATION OF SILICON-CONTAINING SPECIES 13

Table 1.3. Silicon-Based Radical Names

Structure Name
H3Si- silyl
H3Si-SiH2- disilanyl
H3Si-0- siloxy
H3Si-S- silylthio
H3Si-NH- silylamino
H3Si-O-SiH2- disiloxanyl
H3Si-O-SiH2- .O- disiloxanoxy
Me3Si trimethylsilyl
Adapted from Ref. 13, with permission. Copyright Colin
Eaborn.

R
instance, 1-1 is D3D (Chart 1-3).
-
group is replaced by a different residue, this is indicated by a superscripted
symbol. Thus DH re resents OSiMeH , MPhrepresents OSiMe2Ph. For N

M D T Q
silicones silsesquioxanes silicates
poly(dialkylsi1oxanes) silica etc.
Chart 1-2

Me,SiO
Me,SiOSiMe, MM Me S i O i & .
M8,SiO 0 1
.
0
-
-d d < ‘IMe,
OSiMe,
M3QDTM2

0
Me,Si(OSiMe,),,OSiMe, MD,,M
Me,Si’
I
0, ‘TiMe,
-0
SiMe,
D3 - si
,o; -,si
si ,
OLo L si ’ D,D~

I I H
1-1

Chart 1-3

1.4. NMR CHARACTERIZATION OF SILICON-CONTAINING SPECIES

A description of the available spectroscopic (e.g., infrared), spectrometric

(e.g., mass spectrometry), and wet analytical techniques for the characteriza-
tion of silicon-containing compounds is beautifully described in the
authoritative review edited by Smith.’’ The most important of these techniques
in the author’s view is nuclear magnetic resonance (NMR) for: (1) its simplicity;
14 ORGANOSILANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

(2) the amount of information gained; and (3) the nondestructive nature of the
technique.
Several excellent reviews on silicon NMR have appeared in different
monographs.’6-21 Although useful information on the structure of silanes may
be obtained from ‘H NMR and I3C NMR, usually the information provided by
them cannot match that of 29SiNMR. An outline of the possibilities of 29SiNMR
is provided in the following section: A brief presentation of the most frequently
used techniques will be given, followed by some selected tables of data.

1.4.1. *’Si NMR Solution Spectra

The 29Si isotope is the only naturally occurring, NMR-active silicon isotope. It
has a spin quantum number I = - 1/2 and, unfortunately, a natural abundance of
only about 4.7%.20 The problem of low abundance is made worse by the fact that
the nucleus is relatively insensitive. For many years, these two factors severely
limited the use of 29Si NMR. However, with the advent of Fourier transform
spectrometers (FT) and the development of novel pulse sequences, running
silicon spectra is now routine.
While it is possible to do direct acquisition of silicon spectra, this can take
unreasonably long times due to the low sensitivity and abundance of the 29Si
isotope (for instance, delays of >30 seconds between pulses, to allow the nuclei
to relax, may be necessary). Many techniques have been developed to improve
the sensitivity of the 29SiNMR experiment. The simplest of these utilizes a para-
magnetic relaxation agent, typically ~r(acac)3.~* A 0.1 % solution of Cr(acac)s in
the NMR solvent can lead to decreases in acquisition times of at least an order of
magnitude. This is particularly useful for samples that do not contain protons
coupled to the silicon nuclei (see below). Another advantage of these relaxation
agents is that they remove nuclear Overhauser effects (nOe) in the spectra. The
negative nOe normally found with silicon may lead to a decrease of sensitivity
or, in some cases, complete cancellation of the signal (full nOe generates a
-2.52 enhancement for a net gain of ca. - 1.5 times the signal).20Unhelpful
background signals can be avoided by using non-glass NMR tubes and silicon-
free probes when looking at Q-rich samples. Tubes made from Teflon@ or
fluorinated ethylene /polypropylene may successfully be used.20
When one is examining silicon atoms with protons nearby (“J-coupled
protons,” Si-H, Si-CH3, etc.), it is possible to use pulse sequences that utilize
polarization transfer to enhance the rate of acquisition of data. Techniques based
on this approach take advantage of the fast relaxation and high sensitivity of
protons that are coupled to the silicon nuclei. Chemically different silicon atoms
may respond very differently to a given set of parameters in these experiments:
An incorrect choice of coupling constant can lead to the disappearance of peaks,
Note that Q compounds (noncoupled) would not be seen in these experiments
(see above).
Two polarization transfer techniques that are commonly used are INEPT
(Insensitive Nuclei Enhanced by Polarization Transfer) and DEFT (Distortion-
 NMR CHARACTERIZATION OF SILICON-CONTAININGSPECIES 15

Table 1.4. Enhancement of "SI Resonance by Polarization

lhnsfer
~~ ~

Enhancement Chemical shift

Compound (experimental) (~pprn)

Et3SiH 3.6 0.28

Ph2SiHz 5.0 -33.19
(Et0)3SiH 3.6 - 58.82
(HMe2Si)zO 5.1 - 4.42
(Me3SiOMe2Si)0 6.5 7.17
(Me3SiOMezSi)0 6.2 - 21.66
(Me0)Si 5.5 - 78.25
(Me2SiO)5 7.1 -21.14
Me4Si 9.3 0
Me3SiC1 7.5 29.87
MezSiC12 4.8 31.66
MeSiC13 2.9 12.34
t-BuSiCl3 3.6 17.75
f-BuMeSiC12 4.9 36.85
t-Bu2SiF2 5.8 - 7.76
Adapted from Ref. 21 with permission. Copyright 1984
Academic Press.

less Enhancement by Polarization Transfer).23Reported signal enhancements in

the INEPT experiment for some organosilanes may be found in Table 1.4 along
with the chemical shift of the silicon and the Si-H coupling constants
(Table lS).*l Note that the 2Jsi-Hcoupling constants are much smaller than the
lJSi-H coupling constants. In methylsilicones, the 2JSi-H is typically 7 Hz. For
the purposes of comparison, a standard acquisition of Me3SiI would take about
200 scans (at 2 s / scan for M 200 mg of material). Using INEPT, a spectrum
[either decoupled (1 line) or coupled (10 line)] with the same signal-to-noise
ratio could be acquired in 10-20 scans. Larger enhancements are commonly
observed when the coupled H is directly bonded to Si, for example, with HSiC13.
Further structural information may be gained from the use of two-
dimensional (2D) NMR experiments. While well developed for 13C NMR and
'H NMR (COSY, NOESY, e t ~ . ~these ~ ) , techniques have come more recently to
29Si NMR. Two such techniques include HSQC (Heteronuclear Single bond
Quantum Correlation) and HMBC (HeteronuclearMultiple Bond C ~ r r e l a t i o n ) . ~ ~
Using these experiments, connectivity from silicon along several bonds can be
established. This is demonstrated in the spectrum of isomers 1-2and 1-3shown
in Fi ure 1.1. Part of the 'H NMR spectrum is shown in the horizontal spectrum.
The f9Si NMR spectrum is shown on the vertical axis. Hydrogen atoms that are
bonded to carbons proximal to silicon are indicated by the cross peaks (circles)
shown in the middle of the figure. It may be seen that there are two discrete rows
of crosspeaks. Each row represents the hydrogen signals that are coupled to a
16 ORGANOSIIANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

PPm 6 5 4 3

%INMR signal at:

5.04 5.96

Figure 11. 2D HMBC spectrum of 1-2 and 1-3. Reproduced with permission from Ref. 25.
Copyright 1996 American Chemical S~ciety.’~

given silicon resonance. The 29Si NMR resonance at 5.04 [l-2,intensity 1,

representing two isomers, (RRR),(SSS)] couples to one proton in each of the
H(1), H(2), and H(3) environments, while the resonance at 5.96 couples to the
H(1), H(2), and H(3) environments of the other diastereomer [l-3, permutations
of (RRS), (SSR), intensity 31.

1.4.2. *’Si NMR Solid-state Spectra: Magic-Angle Spinning

With the advent of “magic-angle spinning” (MAS) techniques, it is now
possible to acquire excellent spectra from solid materials. These can be done in
 NMR CHARACTERIZATION OF SILICON-CONTAININGSPECIES 17

normal Fourier transform (superconducting) NMR instruments designed for

liquids, with special probes, or dedicated solid-state instruments. By spinning
the samples extremely quickly (2-10 kHz) and orienting the spinning sample at
the magic angle to the applied magnetic field (54.7"), which reduces the

FTMAS CPMAS

(a) 600 (b) 400'

Figure1.2. *'Si NMR of sol-gel prepared silica, cured at (a) 60°C and (b, c) 400°C. Reproduced
with permission from Ref. 28. Copyright Materials Research Society.
Table 1.5. Some 'Jsl-" and 'Jsl-c Coupling Constants
Compound 'J 'J (SiH)29 Other J'' 'J(s~c)'~
HSiF3 -381.7
HSi(OEt)3 - 287 3.4 (3Jsi-~)
H3SiF - 229
H4Si - 202.5
H3SiMe - 194
H2SiMe2 - 188.6
H2SiPhz 198.3 5.9 (ortho)
1 .O (meta)
HSiEt3 185 6.9 ('JSidH)
HSi(SiMe3)3 - 155
MeSiC13 8.1 86.6
H2C=CHSiC13 113
MeSi(OEt), 96.2
MezSi(OEt)z 73
t-Bu2SiF2 325.3 ('Jsi-~)
6.3 ( 3 J s i - ~ )
(Me2SiO)s 7.4
Me2SiC12 7.3 68.3
Me3SiC1 6.8
Me3SiOEt 59
Me2Si(SiMe3)2 37
HC =C-SiEt3 75
Adapted with permission from Ref. 21 (Copyright 1984 Academic Press) and Ref. 29 (Copyright
1989 John Wiley and Sons).
18 ORGANOSIIANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

PPm

-loo I
-80 -
X = NMe2 A

-60 - X=OMe
X=CI

- 40 - X=F
X=Br
0
0
bsi
-20 -

0 I

20 -
40 I I I I
1 2 3 4
n-
Flgure 1.3. "Si chemical shift ranges of Me,SiX4-, relative to SiMe4.33 Reproduced with
permission from Ref. 33. Copyright 1989 John Wiley and Sons.

Table 1.6. %I NMR of Some Simple Silanes

Compound &i (PP~) Compound b i (PP~)

(Me0)3SiMe - 39.8 (Me0)3SiH - 59.4
Me3SiSiMe3 - 19.8 Me3SiSiMe2H - 39.1
C13SiMe 12.47 C13SiH - 9.6

Adapted with permission from Ref. 29. Copyright 1989 John Wiley and Sons.

chemical shift anisotropy, quadrapolar broadening, etc., high-resolution spectra

can be acquired in a reasonable time.26 In essence, rapid spinning leads to an
isotropic averaging of the chemical shift in the solid, a situation similar to that in
solution.27As an example, the degree of conversion, in the acid-catalyzed sol-gel
preparation of silica from Si(OEt)4 (Figure 1.2A; see Chapter lo), is directly
 NMR CHARACTERIZATION OF SILICON-CONTAINING SPECIES 19

available from 29Si NMR: Heating the sample leads to conversion of partly
condensed silica Si(OEt), (QO), SiOSi(OEt), (Q'), . . ,, into Q4(Figure 1.2B).28

1.4.3. Coupling Constants

The magnitude of coupling constants drops off precipitously for long-range
coupling: l ~ S i H>> *JS~H M ,JSiH. However, large variations also arise as a func-
tion of the electronegativity of the other ligands on silicon. Some examples of
'Js~H,'JsiH, and ,&iH coupling constants to hydrogen and carbon, respectively,
are given in Table 1.5.

1.4.4. *'Si NMR Chemical Shift Ranges for Various Organosilanes

The chemical shift range for silicon is very large (- 180 to 250ppm). Thus 29Si
NMR chemical shifts are ve diagnostic. However, determining the electronic
7
distribution at silicon from Si NMR spectra is difficult. It can be seen from
Figure 1.3, for instance, that chemical shifts increase and then decrease as

Table 1.7. 2sSiNMR of Somelhnsition Metal-ContainingSilanes

Compound &i (PP~) Compound &i (PP~)

- 20.9436 145.337

32.4,34.6g40 [M~~J..;.";I'~~~,
PMe, SE' 259.441
20 ORGANOSILANES: WHERE TO FIND THEM, WHAT TO CALL THEM, HOW TO DETECT THEM

methyl groups in SiMe4 are systematically replaced by electronegative groups

such as chlorine. Some general comments, however, may be made: (1)
Substituting methyl groups with hydrogen or with 7r systems leads to an upfield
shift in the signal (Table 1.6); (2) a change in chemical shift accompanies
coordination expansion (for example, the conversion of MeHSi(0Tf )2 to
MeHSi(0Tf )2X(X = -OTf, N-methylimidazole, HMPA) causes an upfield shift
of between 40 and 60 ppm (-9 + -52 to 68 ppmP0); and (3) steric
encumbrance can further alter chemical shifts, as shown from a series of
trimethylsiloxy steroid^.^' This was interpreted to result from the accessibility of

Table 1.8. *'SI NMR Chemical Shifts of "Reactive Silicon Species"

Chemical shift Chemical shift

Compound (PPd Compound (PPm)
I I
Silirane: - 59.847 Silirene: - 1 0 2 . 1 ~ ~
/S'\

Silylium ion: 2251.5~~Ph,SiLi*THF Silyl anion: - g5*

F (PhMe2Si)zCuLi.THF Silyl anion: - 24.453

Disilene: 63.654 @si\

Silaallene: 48A5'

,.*
A Me,Si,
Silene: Si=C ~ 4 . 2 ~ 7-
~
Me$
2- B OSiMe,
C
Silene: A - 12.1;B
41.4; C 13.456

- 29.657
9\ -53d7

- 89.258 [ fi] 2
-196.859

-87.l6'
 -
+ 40 0
SC29 NMR CHEMICAL SHIFT CORRELATION CHART

- 20
UsSdNuez b
-4b 1
-60 - -1 0 ppm

1 s(-N COMPOUNDS

1 SELECTED

+40 + 20 0
I-.
- 20
1 . I
-40
. I
-60
t
-80
l
-100
. 1
-120 ppm

Figure1.4. 29Sichemical shift correlation chart for functional silane and siloxane compounds.66Reproducedwith permission from Ref. 66. Copyright 1991
John Wiley and Sons.
N
Iu
Iu

+a- m 1 ' 1
0
. f .
-20 -40 -
Si-29 NMR CHEMICAL SHIFT CORRELATION CHART

-60
, .
-100
m
-120 ppm

F QENERAUZED
DISILOXANE

r . , . , 1 - i
+40 +20 0 -20 -40 -$o -80 -xK) -120 ppm

Flgure1.5. "Si chemical shift correlation chart for organosilicon compound^.^' Prf = (CH,)&Fs, Z = H, R (alkyl) or OR, R = H, alkyl or functional group,
oxime= R&=N-O-, Q' =(R0)3Si(OH), Q'=(R0)2Si (OH)p,etc. Reproduced with permission from Ref. 67. Copyright 1991 John Wiley and Sons.
 REFERENCES 23

the oxygen carrying silicon: Solvent and other molecular associations modify the
chemical shift. Such effects may be generally responsible for chemical shift
differences between subtly different silyl groups in silicones.32 Some chemical
shifts of the less usual transition metal-containing organosilanes (Table 1.7; see
Chapter 6) and compounds related to reactive intermediates (Table 1.8; see
Chapter 3) are provided.

1.4.5. *’Si NMR Chemical Shift Ranges for Organosilicon Polymers

Charts indicating the typical chemical shifts of organosilanes related to silicones
(Figure 1.4) and organosilicon polymer fragments (Figure 1S ) are shown. 29Si
NMR is particularly sensitive to sequence distributions of different siloxane
units in a silicone copolymer. For instance, the degree of “blockyness” of a
copolymer of dimethyl- and methylphen lsiloxanes could be clearly seen using a
pentad analysis. Thus DPhDPhD DPhDg h at - 20.82 ppm can be distinguished
from DDDDD at -21.91 ~ p m . ’ ~29Si , ~ ‘ NMR may also be used for end group
analysis in silicones and polysilanes. The sensitivity in the chemical shift of
silicon in a pol silane near the terminus can be seen from Chart 1-4.62Similarly,
3D networks,6rsilica,64and ceramics such as silicon carbide and nitride65may
be characterized by 29SiNMR (Figure 1.2). Condensation (sol-gel) reactions can
also be followed using NMR experiments with other nuclei ( 1 7 0 NMR monitors
water, I3C NMR follows MeOH and Me&, and the silicate can be examined by
2 9 ~NMR~*).
i
Chemical Shift

-43.3 -37.9

-15 -39.2
Chart 1-4

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