Organosilicon

A carbon–silicon bond present in all organosilicon compounds

Organosilicon compounds are organic compounds containing carbon–silicon bonds. Organosilicon chemistry is the corresponding science exploring their properties and reactivity. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable. The first organosilicon compound, tetraethylsilane, was discovered by Charles Friedel and James Crafts in 1863 by reaction of tetrachlorosilane with diethylzinc. The carbosilicon silicon carbide is an inorganic compound.

Occurrence and applications

Organosilicon compounds are widely encountered in commercial products. Most common are sealants, caulks, adhesives, and coatings made from silicones.

Silicone caulk, commercial sealants, are mainly composed of organosilicon compounds.
Polydimethylsiloxane (PDMS) is the principal component of silicones.

Biology and medicine

Carbon–silicon bonds are however generally absent in biochemical processes,[1] although their fleeting existence has been reported in a freshwater alga.[2] Silafluofen is an organosilicon compound that functions as a pyrethroid insecticide. Several organosilicon compounds are being investigated as pharmaceuticals.[3]

Properties of Si–C, Si–O, and Si–F bonds

In most organosilicon compounds, Si is tetravalent and tetrahedral. Carbon–silicon bonds compared to carbon–carbon bonds are longer (186 pm vs. 154 pm) and weaker with bond dissociation energy 451 kJ/mol vs. 607 kJ/mol.[4] The C–Si bond is somewhat polarised towards carbon due to carbon's greater electronegativity (C 2.55 vs Si 1.90). The Si–C bond can be broken more readily than typical C–C bonds. One manifestation of bond polarization in organosilanes is found in the Sakurai reaction.[5] Certain alkyl silanes can be oxidized to an alcohol in the Fleming–Tamao oxidation.

Another manifestation is the β-silicon effect describes the stabilizing effect of a β-silicon atom on a carbocation with many implications for reactivity.

Si–O bonds are much stronger (809 kJ/mol compared to 538 kJ/mol) than a typical C–O single bond. The favorable formation of Si–O bonds drive many organic reactions such as the Brook rearrangement and Peterson olefination. Compared to the strong Si–O bond, the Si–F bond is even stronger.

Production

The bulk of organosilicon compounds derive from organosilicon chlorides (CH3)4-xSiClx. These chlorides produced by the "Direct process", which entails the reaction of methyl chloride with a silicon-copper alloy. The main and most sought-after product is dimethyldichlorosilane:

2 CH3Cl + Si → (CH3)2SiCl2

A variety of other products are obtained, including trimethylsilyl chloride and methyltrichlorosilane. About 1 million tons of organosilicon compounds are prepared annually by this route. The method can also be used for phenyl chlorosilanes.[6]

Hydrosilylation

Compounds with Si-H bonds add to unsaturated substrates in the process called hydrosilylation (also called hydrosilation).[7] Commercially, the main substrates are alkenes. Other unsaturated functional groups—alkynes, imines, ketones, and aldehydes—also participate, although these uses are rather specialized. An example is the hydrosilation of phenylacetylene:[8]

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

Functional groups

Silanols, siloxides, and siloxanes

Silanols are analogues of alcohols. They are generally prepared by hydrolysis of silyl chlorides and oxidation of silyl hydrides:[9]

R3SiCl + H2O → R3SiOH + HCl

Less frequently they are prepared by oxidation of silyl hydrides:

2 R3SiH + O2 → 2R3SiOH

The parent R3SiOH is too unstable for isolation, but the many organic derivatives are known including (CH3)3SiOH and (C6H5)3SiOH. They are about 500x more acidic than the corresponding alcohols. Siloxides (silanoates) are the deprotonated derivatives of silanols:[9]

R3SiOH + NaOH → R3SiONa + H2O

Silanols tend to dehydrate to give siloxanes:

2 R3SiOH → R3Si-O-SiR3 + H2O

Polymers with repeating siloxane linkages are called silicones. Compounds with an Si=O double bond called silanones are extremely unstable.

Silyl ethers

Silyl ethers have the connectivity Si-O-C. They are typically prepared by the reaction of alcohols with silyl chlorides:

(CH3)3SiCl + ROH → (CH3)3Si-O-R + HCl

Silyl ethers are extensively used as protective groups for alcohols.

Exploiting the strength of the Si-F bond, fluoride sources such as tetra-n-butylammonium fluoride (TBAF) are used in deprotection of silyl ethers:

CH3)3Si-O-R + F− + H2O → (CH3)3Si-F + H-O-R + OH−

Silyl chlorides

Organosilyl chlorides are important commodity chemicals. They are mainly used to produce silicone polymers as described above. Especially important silyl chlorides are dimethyldichlorosilane (Me2SiCl2), methyltrichlorosilane (MeSiCl3), and trimethylsilyl chloride (Me3SiCl). More specialized derivatives that find commercial applications include dichloromethylphenylsilane, trichloro(chloromethyl)silane, trichloro(dichlorophenyl)silane, trichloroethylsilane, and phenyltrichlorosilane.

Although proportionately a minor outlet, organosilicon compounds are widely used in organic synthesis. Notably trimethylsilyl chloride Me3SiCl is the main silylating agent. One classic method called the Flood reaction for the synthesis of this compound class is by heating hexaalkyldisiloxanes R3SiOSiR3 with concentrated sulfuric acid and a sodium halide.[10]

Silyl hydrides

Main article: Silyl hydride

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 electronegative than silicon hence the naming convention of silyl hydrides. Commonly the presence of the hydride is not mentioned in the name of the compound. Triethylsilane has the formula Et3SiH. Phenylsilane is PhSiH3. The parent compound SiH4 is called silane.

Silanylidenes

Main article: Silanylidene group

Silanylidenes are compounds containing a silicon based chain, joined by a double bond to the main molecule, such as silylidenemethanol. Where it is the main functional group, the molecule is named after the parent silane, with the -ylidene- infix, such as methylidenesilane.

Silenes

Organosilicon compounds, unlike their carbon counterparts, do not have a rich double bond chemistry due to the large difference in electronegativity.[11] Existing compounds with silene Si=C bonds (also known as alkylidenesilanes) are laboratory curiosities such as the silicon benzene analogue silabenzene. In 1967, Gusel'nikov and Flowers provided the first evidence for silenes from pyrolysis of dimethylsilacyclobutane.[12] The first stable (kinetically shielded) silene was reported in 1981 by Brook [13] [14]

Disilenes have Si=Si double bonds and disilynes are silicon analogues of an alkyne. The first Silyne (with a silicon to carbon triple bond) was reported in 2010 [15]

Siloles

Chemical structure of silole

Siloles, also called silacyclopentadienes, are members of a larger class of compounds called metalloles. They are the silicon analogs of cyclopentadienes and are of current academic interest due to their electroluminescence and other electronic properties.[16][17] Siloles are efficient in electron transport. They owe their low lying LUMO to a favorable interaction between the antibonding sigma silicon orbital with an antibonding pi orbital of the butadiene fragment.

Hypercoordinated silicon

Unlike carbon, silicon compounds can be coordinated to five atoms as well in a group of compounds ranging from so-called silatranes, such as phenylsilatrane, to a uniquely stable pentaorganosilicate:[18]

The stability of hypervalent silicon is the basis of the Hiyama coupling, a coupling reaction used in certain specialized organic synthetic applications. The reaction begins with the activation of Si-C bond by fluoride:

R-SiR'3 + R"-X + F− → R-R" + R'3SiF + X−

Various reactions

Certain allyl silanes can be prepared from allylic ester such as 1 and monosilylcopper compounds such as 2 in.[19][20]

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.

See also

CH He
CLi CBe CB CC CN CO CF Ne
CNa CMg CAl CSi CP CS CCl CAr
CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr CKr
CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI CXe
CCs CBa CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn
Fr CRa Rf Db CSg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
↓
CLa CCe CPr CNd CPm CSm CEu CGd CTb CDy CHo CEr CTm CYb CLu
Ac CTh CPa CU CNp CPu CAm CCm CBk CCf CEs Fm Md No Lr
Chemical bonds to carbon
Core organic chemistry Many uses in chemistry
Academic research, but no widespread use Bond unknown

References

  1. ↑ Organosilicon Chemistry S. Pawlenko Walter de Gruyter New York 1986
  2. ↑ Stephen D. Kinrade, Ashley-M. E. Gillson and Christopher T. G. Knight (2002), Silicon-29 NMR evidence of a transient hexavalent silicon complex in the diatom Navicula pelliculosa. J. Chem. Soc., Dalton Trans., 307–309, doi:10.1039/b105379p
  3. ↑ Bains, W.; Tacke, R. "Silicon chemistry as a novel source of chemical diversity in drug design" Curr Opin Drug Discov Devel. 2003 Jul;6(4):526-43.
  4. ↑ Handbook of Chemistry and Physics, 81st Edition CRC Press ISBN 0-8493-0481-4
  5. ↑ Silicon in Organic Synthesis Colvin, E. Butterworth: London 1981
  6. ↑ Röshe, L.; John, P.; Reitmeier, R. “Organic Silicon Compounds” Ullmann’s Encyclopedia of Industrial Chemistry, 2003, Wiley-VCH, Weinheim. doi:10.1002/14356007.a24_021.
  7. ↑ B. Marciniec (ed.), Hydrosilylation, Advances in Silicon Science, DOI 10.1007/978-1-4020-8172-9 1, C Springer Science+Business Media B.V. 2009.
  8. ↑ 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
  9. 1 2 Paul D. Lickiss "The Synthesis and Structure of Organosilanols" Advances in Inorganic Chemistry Volume 42, 1995, Pages 147–262 doi:10.1016/S0898-8838(08)60053-7
  10. ↑ Preparation of Triethylsilicon Halides E. A. Flood J. Am. Chem. Soc.; 1933; 55(4) pp 1735 - 1736; doi:10.1021/ja01331a504
  11. ↑ Silylenes, Silenes, and Disilenes: Novel Silicon-Based Reagents for Organic Synthesis? Henrik Ottosson and Patrick G. Steel Chem. Eur. J. 2006, 12, 1576–1585 doi:10.1002/chem.200500429
  12. ↑ The thermal decomposition of 1,1-dimethyl-1-silacyclobutane and some reactions of an unstable intermediate containing a silicon–carbon double bond L. E. Gusel'Nikov and M. C. Flowers Chem. Commun. (London), 1967, 864 - 865, doi:10.1039/C19670000864
  13. ↑ A solid silaethene: isolation and characterization Adrian G. Brook, Fereydon Abdesaken, Brigitte Gutekunst, Gerhard Gutekunst and R. Krishna Kallury J. Chem. Soc., Chem. Commun., 1981, 191 - 192, doi:10.1039/C39810000191
  14. ↑ Brook silenes: inspiration for a generation Kim M. Baines Chem. Commun., 2013,49, 6366-6369 doi:10.1039/C3CC42595A
  15. ↑ Gau, D., Kato, T., Saffon-Merceron, N., De Cózar, A., Cossío, F. and Baceiredo, A. (2010), Synthesis and Structure of a Base-Stabilized C-Phosphino-Si-Amino Silyne. Angewandte Chemie International Edition, 49: 6585–6588. doi:10.1002/anie.201003616
  16. ↑ Direct synthesis of 2,5-dihalosiloles Organic Syntheses 2008, 85, 53-63 http://www.orgsynth.org/orgsyn/pdfs/V85P0053.pdf
  17. ↑ Synthesis of new dipyridylphenylaminosiloles for highly emissive organic electroluminescent devices Laurent Aubouy, Philippe Gerbier, Nolwenn Huby, Guillaume Wantz, Laurence Vignau, Lionel Hirsch and Jean-Marc Jano New J. Chem., 2004, 28, 1086 - 1090, doi:10.1039/b405238b
  18. ↑ 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
  19. ↑ 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
  20. ↑ 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

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