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'''Organosilicon compounds''' are [[chemical compound]]s containing [[carbon]] [[silicon]] [[chemical bond|bonds]]. '''Organosilicon chemistry''' is the corresponding science exploring the properties and reactivity of organosilicon compounds <ref>''Silicon in Organic Synthesis'' Colvin, E. Butterworth: London 1981</ref>. Most of organosilicon compounds are [[tetravalent]] and [[tetrahedral molecular geometry|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]]. <ref>Herreros B. et al., Science, 1994, 263, 1585-1587.</ref> In aqueous solution, the hexaoxo-center is documented only for complexes in which silicon is chelated by catechol (yielding tris[1,2-benzenediolato]silicate) <ref>A. Rosenheim, B. Reibmann, G. Schendel, Z. Anorg. Chem. 1931, 196, 160.</ref> <ref>I. F. Sedeh, S. Sjöberg, L. O. Öhman, Acta Chem. Scand. 1992, 46, 933.</ref> <ref>I. F. Sedeh, S. Sjöberg, L. O. Öhman, J. Inorg. Biochem. 1993, 50, 119.</ref>, 2-hydroxypyridine N-oxide <ref>A. Weiss, D. R. Harvey, 1964, Angew. Chem. 76, 818.</ref>, tropolone <ref>S. Sjöberg, N. Ingri, A. M. Nenner, L. O. Öhman, J. Inorg. Biochem. 1985, 24, 267</ref>, or closely related analogs; pentaoxosilicon is unknown until recently. <ref>Kinrade, S. D. et al. Science, 1999, 285, 1542-1545.</ref>
'''Organosilicon compounds''' are [[chemical compound]]s containing [[carbon]] [[silicon]] [[chemical bond|bonds]]. '''Organosilicon chemistry''' is the corresponding science exploring the properties and reactivity of organosilicon compounds <ref>''Silicon in Organic Synthesis'' Colvin, E. Butterworth: London 1981</ref>. Most of organosilicon compounds are [[tetravalent]] and [[tetrahedral molecular geometry|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]]. <ref>Herreros B. et al., Science, 1994, 263, 1585-1587.</ref> In aqueous solution, the hexaoxo-center is documented only for complexes in which silicon is chelated by catechol (yielding tris[1,2-benzenediolato]silicate) <ref>A. Rosenheim, B. Reibmann, G. Schendel, Z. Anorg. Chem. 1931, 196, 160.</ref> <ref>I. F. Sedeh, S. Sjöberg, L. O. Öhman, Acta Chem. Scand. 1992, 46, 933.</ref> <ref>I. F. Sedeh, S. Sjöberg, L. O. Öhman, J. Inorg. Biochem. 1993, 50, 119.</ref>, 2-hydroxypyridine N-oxide <ref>A. Weiss, D. R. Harvey, 1964, Angew. Chem. 76, 818.</ref>, tropolone <ref>S. Sjöberg, N. Ingri, A. M. Nenner, L. O. Öhman, J. Inorg. Biochem. 1985, 24, 267</ref>, or closely related analogs; pentaoxosilicon is unknown until recently. <ref>Kinrade, S. D. et al. Science, 1999, 285, 1542-1545.</ref>


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Carbon silicon bonds compared to carbon carbon bonds are longer (186 [[picometer|pm]] vs. 154 pm) and weaker with [[bond dissociation energy]] 451 [[KJ]]/[[mole (unit)|mole]] vs 607 KJ/mol <ref>''Handbook of Chemistry and Physics'', 81st Edition CRC Press ISBN 0-8493-0481-4</ref>. 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]].  
Carbon silicon bonds compared to carbon carbon bonds are longer (186 [[picometer|pm]] vs. 154 pm) and weaker with [[bond dissociation energy]] 451 [[KJ]]/[[mole (unit)|mole]] vs 607 KJ/mol <ref>''Handbook of Chemistry and Physics'', 81st Edition CRC Press ISBN 0-8493-0481-4</ref>. 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  <ref>''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}}--></ref> <ref> By [[isotope labeling|isotopic]] [[desymmetrisation]] on the substrate (replacing hydrogen by [[isotope labeling|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|oxidative addition / reductive elimination]] step</ref>.
Certain [[allyl]] silanes can be prepared from allylic [[ester]] such as '''1''' and monosilylcopper compounds such as '''2''' in  <ref>''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</ref> <ref> By [[isotope labeling|isotopic]] [[desymmetrisation]] on the substrate (replacing hydrogen by [[isotope labeling|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|oxidative addition / reductive elimination]] step</ref>.
:   
:   


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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 agent]]s for example [[PMHS]].  
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 agent]]s for example [[PMHS]].  


In one study triethylsilylhydride is used in the conversion of an [[phenyl azide]] to an [[aniline]] <ref>''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}}</ref>:
In one study triethylsilylhydride is used in the conversion of an [[phenyl azide]] to an [[aniline]] <ref>''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</ref>:


<!--:[[Image:AzideReductionByTriethylsilylhydride.png|400px|Azide Reduction By Triethylsilylhydride]]-->
<!--:[[Image:AzideReductionByTriethylsilylhydride.png|400px|Azide Reduction By Triethylsilylhydride]]-->
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Silyl hydrides can even take up the reduction of robust molecules such as [[carbon dioxide]] (to [[methane]]) <ref>''From Carbon Dioxide to Methane: Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium-Borane Complexes''
Silyl hydrides can even take up the reduction of robust molecules such as [[carbon dioxide]] (to [[methane]]) <ref>''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}}</ref>:  
Tsukasa Matsuo and Hiroyuki Kawaguchi [[J. Am. Chem. Soc.]]; '''2006'''; 128(38) pp 12362 - 12363; DOI 10.1021/ja0647250</ref>:  


<!--:[[Image:Carbondioxidereduction.png|400px|Carbon dioxide reduction]]-->
<!--:[[Image:Carbondioxidereduction.png|400px|Carbon dioxide reduction]]-->
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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.
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
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


1962 Henry Gilman
==Attribution==
{{WPAttribution}}


1963 Leo H. Sommer
==References==
<small>
<references>


1964 Colin Eaborn
</references>
</small>


1965 Eugene G. Rochow


1966 Gerhard Fritz
[[Category:Suggestion Bot Tag]]
 
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
 
== See also ==
* Compounds of carbon with [[period 3 element]]s: '''organosilicon compounds''', [[organophosphorus compound]]s, [[organosulfur compound]]s,
* Compounds of carbon with other [[carbon group|group 14]] elements: '''organosilicon compounds''', [[organogermanium compound]]s, [[organotin compound]]s, [[organolead compound]]s.
* [[silylene]]s, the [[carbene]] counterparts and [[silylenoid]]s the carbenoid counterparts.
 
== References ==
{{reflist|2}}[[Category:Suggestion Bot Tag]]

Revision as of 09:13, 13 October 2024

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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

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

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

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

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

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

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

References

  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

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