Organosilicon



Organosilicon compounds are biomolecule [2].

The first organosilicon compound, tetraethylsilane was discovered by Charles Friedel and 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 Hiyama coupling.

Certain ester such as 1 and monosilylcopper compounds such as 2 in [4] [5].

In this reaction type silicon polarity is reversed in a chemical bond with benzoyloxy group takes place.

The chemistry of 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 Peterson olefination.

Another manifestation is the highly explosive nature of the silicon pendant of pentaerytritol tetranitrate [6] [7]:

A single crystal of this compound, first synthesized in 2007 even detonates when in contact with a teflon spatula and in fact made full characterization impossible. Another contributor to its exothermic decomposition (inferred from much safer in silico experimentation) is the ability of silicon in its crystal phase to coordinate to two oxygen nitrito groups in addition to regular coordination to the four carbon atoms. This additional coordination would make formation of silicon dioxide (one of the decomposition products) more facile.

Silyl halides

Organosilyl halides are important reagents in organic chemistry notably halide [8]. Other relevant silyl halides are dichloromethylphenylsilane, dimethyldichlorosilane, methyltrichlorosilane, (4-aminobutyl)diethoxymethylsilane, trichloro(chloromethyl)silane, trichloro(dichlorophenyl)silane, trichloroethylsilane, trichlorophenylsilane and trimethylchlorosilane

Silyl hydrides

The silicon to hydrogen bond is longer than the C–H bond (148 compared to 105 pm) and weaker (299 compared to 338 kJ/mol). Hydrogen is more reducing agents for example PMHS.

In one study triethylsilylhydride is used in the conversion of an aniline [9]:

In this reaction ACCN is a catalytic cycle:

Aqueous workup then gives aniline.

Silyl hydrides can even take up the reduction of robust molecules such as carbon dioxide (to methane) [10]:

Although it takes a very complex catalyst system.

Hydrosilylation

Silyl hydrides react with various unsaturated substrates such as trans or cis or the geminal vinyl silane, for example [11]:

In the related silylmetalation, a metal replaces the hydrogen atom.

Silenes

Organosilicon compounds unlike their carbon counterparts do not have a rich disilenes.

Hypercoordinated silicon

Unlike carbon, silicon compounds can be coordinated to five atoms as well in a group of compounds ranging from so-called silatranes to a uniquely stable pentaorganosilicate [12]:

See also

CH He
CLi CBe CB CC CN CO CF Ne
CNa CMg CAl CSi CP CS CCl Ar
CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr Kr
CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI Xe
CCs CBa CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa CU Np Pu Am Cm Bk Cf Es Fm Md No Lr


carbon
Core organic chemistry many uses in chemistry.
Academic research, but no widespread use Bond unknown / not assessed.

References

  1. ^ Silicon in Organic Synthesis Colvin, E. Butterworth: London 1981
  2. ^ Organosilicon Chemistry S. Pawlenko Walter de Gruyter New York 1986
  3. ^ Handbook of Chemistry and Physics, 81st Edition CRC Press ISBN 0-8493-0481-4
  4. ^ 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
  5. ^ By oxidative addition / reductive elimination step
  6. ^ The Sila-Explosives Si(CH2N3)4 and Si(CH2ONO2)4: Silicon Analogues of the Common Explosives Pentaerythrityl Tetraazide, C(CH2N3)4, and Pentaerythritol Tetranitrate, C(CH2ONO2)4 Thomas M. Klapötke, Burkhard Krumm, Rainer Ilg, Dennis Troegel, and Reinhold Tacke J. Am. Chem. Soc.; 2007; ASAP Web Release Date: 04-May-2007; (Article) doi:10.1021/ja071299p
  7. ^ Sila-Explosives Offer A Better Bang Stephen K. Ritter Chemical & Engineering News May 7 2007Link
  8. ^ Preparation of Triethylsilicon Halides E. A. Flood J. Am. Chem. Soc.; 1933; 55(4) pp 1735 - 1736; doi:10.1021/ja01331a504
  9. ^ 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
  10. ^ 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
  11. ^ Effect of the synthetic method of Pt/MgO in the hydrosilylation of phenylacetylene Eulalia Ramírez-Oliva, Alejandro Hernández, J. Merced Martínez-Rosales, Alfredo Aguilar-Elguezabal, Gabriel Herrera-Pérez, and Jorge Cervantesa Arkivoc 2006 (v) 126-136 Link
  12. ^ Tetraalkylammonium pentaorganosilicates: the first highly stable silicates with five hydrocarbon ligands Sirik Deerenberg, Marius Schakel, Adrianus H. J. F. de Keijzer, Mirko Kranenburg, Martin Lutz, Anthony L. Spek, Koop Lammertsma, Chem. Commun., 2002, (4),348-349 doi:10.1039/b109816k
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Organosilicon". A list of authors is available in Wikipedia.