Organosilicon

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This editable Main Article is under development and subject to a disclaimer.

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## Contents

* 1 Organosilanes
* 2 Siloxides
* 3 Silyl hydrides
* 4 Silenes
* 5 Frederic Stanley Kipping Award in Silicon Chemistry, American Chemical Society
* 6 Attribution
* 7 References

Organosilicon compounds are chemical compounds containing carbon silicon bonds. Organosilicon chemistry is the corresponding science exploring the properties and reactivity of organosilicon compounds [1]. Most of organosilicon compounds are tetravalent and tetrahedral. Hypervalent silicon is rare, and occurs mainly in organosilicon complexes obtained in non-aqueous solutions, in some glasses, and at high pressures within the earth in dense phases such as stishovite. [2] In aqueous solution, the hexaoxo-center is documented only for complexes in which silicon is chelated by catechol (yielding tris[1,2-benzenediolato]silicate) [3] [4] [5], 2-hydroxypyridine N-oxide [6], tropolone [7], or closely related analogs; pentaoxosilicon is unknown until recently. [8]

Unlike carbon, silicon is not found in any biomolecules [9]. However, it was found recently that many sugars could form stable pentavalent and/or hexavalent complexes with silicate in aqueous solution under ambient conditions. [10] This study suggested that silicates might be extensively involved in the prebiotic chemistry.

The first organosilicon compound, tetraethylsilane was discovered by Charles Friedel and James Crafts in 1863 by reaction of tetrachlorosilane with diethyl zinc. Discovered in 1893, the simplest marriage between silicon and carbon is Silicon carbide which has many industrial applications.

## Organosilanes[edit]

Carbon silicon bonds compared to carbon carbon bonds are longer (186 pm vs. 154 pm) and weaker with bond dissociation energy 451 KJ/mole vs 607 KJ/mol [11]. The C-Si is strongly polarized towards carbon due to its higher electronegativity ( C 2.55 vs Si 1.90). One manifestation of bond polarization in organosilanes is found in the Sakurai reaction.

Certain allyl silanes can be prepared from allylic ester such as 1 and monosilylcopper compounds such as 2 in [12] [13].

In this reaction type silicon polarity is reversed in a chemical bond with zinc and a formal allylic substitution on the benzoyloxy group takes place.

The chemistry of silanes such as tetramethylsilane is comparable to that of alkanes in many aspects such as thermal stability. The β-silicon effect describes the stabilizing effect of a β-silicon atom on a carbocation with many implications for reactivity.

## Siloxides[edit]

More notably bonds of silicon to oxygen are much shorter and stronger (809 compared to 538 KJ/mole) than that of those of carbon to oxygen. The polarization in this bond increases towards oxygen. Examples are the Siloxanes and the polymeric polysiloxanes. Silyl ethers are extensively used as protective groups for alcohols. Only silicon bonds to fluorine are stronger and that is why the fluorine source TASF (or more commonly TBAF) is useful in deprotection. The favorable formation of Si-O bonds drive many organic reaction such as the Brook rearrangement and Peterson olefination.

## Silyl hydrides[edit]

The silicon to hydrogen bond is longer than the C-H bond (105 compared to 148 pm) and weaker (338 compared to 299 KJ/mole). Hydrogen is more electronegative than silicon hence the naming convention of silyl hydrides. Silyl hydrides are very reactive and used as reducing agents for example PMHS.

In one study triethylsilylhydride is used in the conversion of an phenyl azide to an aniline [14]:

In this reaction ACCN is a radical initiator and an aliphatic thiol transfers radical character to the silylhydride. The triethylsilyl free radical then reacts with the azide with expusion of nitrogen to a N-silylarylaminyl radical which grabs a proton from a thiol completing the catalytic cycle:

Aqueous workup then gives aniline.

Silyl hydrides can even take up the reduction of robust molecules such as carbon dioxide (to methane) [15]:

Although it takes a very complex catalyst system.

## Silenes[edit]

Organosilicon compounds unlike their carbon counterparts do not have a rich double bond chemistry due to the large difference in electronegativity. Existing compounds with organosilene Si=C bonds are laboratory curiosities such as the silicon benzene analogue silabenzene, and Si=Si bond containing disilenes.

## Frederic Stanley Kipping Award in Silicon Chemistry, American Chemical Society[edit]

The Kipping award was established in 1960 by Dow Corning Corporation to commemorate the achievements of Prof. Frederic Stanley Kipping. It is the most prestigious scientific award in silicon chemistry. The award is to recognize distinguished contributions to the field of silicon chemistry and, by such example, to stimulate the creativity of others. The award consists of $5,000 and a certificate. In 2006, the recipient is Professor Akira Sekiguchi.

Recipients:

* 1962 Henry Gilman
* 1963 Leo H. Sommer
* 1964 Colin Eaborn
* 1965 Eugene G. Rochow
* 1966 Gerhard Fritz
* 1967 Makoto Kumada
* 1968 Ulrich Wannagat
* 1969 Robert A. Benkeser
* 1970 Robert West
* 1971 Alan G. MacDiarmid
* 1972 Dietmar Seyferth
* 1973 Adrian G. Brook
* 1974 Hubert Schmidbaur
* 1975 Hans Bock
* 1976 Michael F. Lappert
* 1978 Hideki Sakurai
* 1980 E. A. V. Ebsworth
* 1982 Thomas J. Barton
* 1984 Robert J. P. Corriu
* 1986 Peter P. Gaspar
* 1988 Raymond Calas
* 1990 John L. Speier, Jr.
* 1992 Nils Wiberg
* 1994 Robin Walsh
* 1996 Wataru Ando
* 1998 Joseph B. Lambert
* 2000 Peter Jutzi
* 2002 Kohei Tamao
* 2004 James E. Mark
* 2006 Akira Sekiguchi

## Attribution[edit]

Some content on this page may previously have appeared on Wikipedia.

## References[edit]

1. ↑ Silicon in Organic Synthesis Colvin, E. Butterworth: London 1981
2. ↑ Herreros B. et al., Science, 1994, 263, 1585-1587.
3. ↑ A. Rosenheim, B. Reibmann, G. Schendel, Z. Anorg. Chem. 1931, 196, 160.
4. ↑ I. F. Sedeh, S. Sjöberg, L. O. Öhman, Acta Chem. Scand. 1992, 46, 933.
5. ↑ I. F. Sedeh, S. Sjöberg, L. O. Öhman, J. Inorg. Biochem. 1993, 50, 119.
6. ↑ A. Weiss, D. R. Harvey, 1964, Angew. Chem. 76, 818.
7. ↑ S. Sjöberg, N. Ingri, A. M. Nenner, L. O. Öhman, J. Inorg. Biochem. 1985, 24, 267
8. ↑ Kinrade, S. D. et al. Science, 1999, 285, 1542-1545.
9. ↑ Organosilicon Chemistry S. Pawlenko Walter de Gruyter New York 1986
10. ↑ Lambert, J. B.; Lu, G.; Singer, S. R.; Kolb, V. M. J. Am. Chem. Soc. 2004, 126, 9611-9625.
11. ↑ Handbook of Chemistry and Physics, 81st Edition CRC Press ISBN 0-8493-0481-4
12. ↑ Mechanistic insight into copper-catalysed allylic substitutions with bis(triorganosilyl) zincs. Enantiospecific preparation of -chiral silanes] Eric S. Schmidtmann and Martin Oestreich Chem. Commun., 2006, 3643 - 3645, DOI 10.1039/b606589a
13. ↑ By isotopic desymmetrisation on the substrate (replacing hydrogen by deuterium) it can be demonstrated that the reaction proceeds not through the symmetrical π-allyl intermediate 5 which would give an equal mixture of 3a and 3b but through the Π-δ intermediate 4 resulting in 3a only, through an oxidative addition / reductive elimination step
14. ↑ Radical Reduction of Aromatic Azides to Amines with Triethylsilane Luisa Benati, Giorgio Bencivenni, Rino Leardini, Matteo Minozzi, Daniele Nanni, Rosanna Scialpi, Piero Spagnolo, and Giuseppe Zanardi J. Org. Chem.; 2006; 71(15) pp 5822 - 5825; (Note) DOI 10.1021/jo060824k
15. ↑ 'From Carbon Dioxide to Methane: Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes Tsukasa Matsuo and Hiroyuki Kawaguchi J. Am. Chem. Soc.; 2006; 128(38) pp 12362 - 12363; DOI 10.1021/ja0647250