Organosilicon chemistry

Polydimethylsiloxane (PDMS) is the principal component of silicones.

Organosilicon chemistry is the study of organometallic compounds containing carbon–silicon bonds, to which they are called organosilicon compounds. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

History

See also: Organometallic chemistry

In 1863, Charles Friedel and James Crafts made the first organochlorosilane compound.^[1] The same year, they also described a "polysilicic acid ether" in the preparation of ethyl- and methyl-o-silicic acid.^[1] Extensive research in the field of organosilicon compounds was pioneered in the beginning of 20th century by Frederic S. Kipping.^[2] He also had coined the term "silicone" (resembling ketones, though this is erroneous)^{[3][4]: 286} in relation to these materials in 1904. In recognition of Kipping's achievements, the Dow Chemical Company had established an award in the 1960s that is given for significant contributions to the field of silicon chemistry.^[5] In his works, Kipping was noted for using Grignard reagents to make alkylsilanes and arylsilanes and preparing silicone oligomers and polymers for the first time.^[2]

In 1945, Eugene G. Rochow also made a significant contribution to the field of organosilicon chemistry by first describing the Müller-Rochow process.^[6]

Occurrence and applications

Silicone caulk, commercial sealants, are mainly composed of organosilicon compounds mixed with hardener.

Organosilicon compounds are widely encountered in commercial products. Most common are antifoamers, caulks (sealant), adhesives, and coatings made from silicones. Other important uses include agricultural and plant control adjuvants commonly used in conjunction with herbicides and fungicides.^[7]

Biology and medicine

Carbon–silicon bonds are absent in biology, however enzymes have been used to artificially create carbon-silicon bonds in living microbes.^[8][9][10] Silicates, on the other hand, have known existence in diatoms.^[11] Silafluofen is an organosilicon compound that functions as a pyrethroid insecticide. Several organosilicon compounds have been investigated as pharmaceuticals.^[12][13]

Bonding

Electronegativities Relevant to Organosilicon Chemistry

C	Si	H	O
2.5	1.8	2.1	3.4

Properties Relevant to Organosilicon Chemistry

Bond	Bond length (pm)	Approx. bond strength (kJ/mol)
C-C	154	334
Si-Si	234	196
C-Si	186	314
C-H	110	414
Si-H	146	314
C-O	145	355
Si-O	159	460

Dissociation energies of bonds to silicon^[14]

Bond	Energy (kJ/mol)
Si–Si	327(10)
Si–Br	343(50)
Si–C	435(21)
Si–Cl	456(42)
Si–F	540(13)
Si–H	298.49(46)
Si–I	339(84)
Si–N	439(38)
Si–O	798(8)
Si–S	619(13)
Si–Se	531(25)
H3Si–SiH3	339(17)
Me3Si–SiMe3	339
Ar3Si–SiAr3	368(31)
Si–Te	506(38)

In the great majority of organosilicon compounds, Si is tetravalent with tetrahedral molecular geometry. Compared to carbon–carbon bonds, carbon–silicon bonds are longer and weaker.^[7][15]

The C–Si bond is somewhat polarised towards carbon due to carbon's greater electronegativity (C 2.55 vs Si 1.90), and single bonds from Si to electronegative elements are very strong.^[14] Silicon is thus susceptible to nucleophilic attack by O⁻, Cl⁻, or F⁻; the energy of an Si–O bond in particular is strikingly high. This feature is exploited in many reactions such as the Sakurai reaction, the Brook rearrangement, the Fleming–Tamao oxidation, and the Peterson olefination.^[16]

The Si–C bond (1.89 Å) is significantly longer than a typical C–C bond (1.54 Å), suggesting that silyl substitutents have less steric demand than their organyl analogues. When geometry allows, silicon exhibits negative hyperconjugation, reversing the usual polarization on neighboring atoms.^{[citation needed]}

Preparation

The first organosilicon compound, tetraethylsilane, was prepared by Charles Friedel and James Crafts in 1863 by reaction of tetrachlorosilane with diethylzinc.

The bulk of organosilicon compounds derive from organosilicon chlorides (CH
₃)
_4-xSiCl
_x. These chlorides are 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 CH
₃Cl + Si → (CH
₃)
₂SiCl
₂

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.^[17]

Hydrosilylation

Main article: Hydrosilylation

Another major method for the formation of Si-C bonds is hydrosilylation (also called hydrosilation).^[18] In this process, compounds with Si-H bonds (hydrosilanes) are added to unsaturated substrates. Commercially, the main substrates are alkenes. Other unsaturated functional groups — alkynes, imines, ketones, and aldehydes — also participate, but these reactions are of little economic value.^[19]

Idealized mechanism for metal-catalysed hydrosilylation of an alkene

Hydrosilylation requires metal catalysts, especially those based on platinum group metals.

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

Cleavage of Si-Si bonds

Hexamethyldisilane reacts with methyl lithium to give trimethylsilyl lithium:^[20]

(CH₃)₆Si₂ + CH₃Li → (CH₃)₃SiLi + (CH₃)₄Si

Similarly, tris(trimethylsilyl)silyl lithium is derived from tetrakis(trimethylsilyl)silane:^[21]

((CH₃)₃Si)₄Si + CH₃Li → ((CH₃)₃Si)₃SiLi + (CH₃)₄Si

Functional groups

Silicon is a component of many functional groups. Most of these are analogous to organic compounds. The overarching exception is the rarity of multiple bonds to silicon, as reflected in the double bond rule.

Silanols, siloxides, and siloxanes

Silanols are analogues of alcohols. They are generally prepared by hydrolysis of silyl chlorides:^[22]

R
₃SiCl + H₂O → R
₃SiOH + HCl

Less frequently silanols are prepared by oxidation of silyl hydrides, a reaction that uses a metal catalyst:

2 R
₃SiH + O
₂ → 2 R
₃SiOH

Many silanols have been isolated including (CH
₃)
₃SiOH and (C
₆H
₅)
₃SiOH. They are about 500x more acidic than the corresponding alcohols. Siloxides are the deprotonated derivatives of silanols:^[22]

R
₃SiOH + NaOH → R
₃SiONa + H₂O

Silanols tend to dehydrate to give siloxanes:

2 R
₃SiOH → R
₃Si-O-SiR
₃ + 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:

(CH
₃)
₃SiCl + ROH → (CH
₃)
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:

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

Silyl chlorides

Main article: Chlorosilane

Organosilyl chlorides are important commodity chemicals. They are mainly used to produce silicone polymers as described above. Especially important silyl chlorides dimethyldichlorosilane (Me
₂SiCl
₂), methyltrichlorosilane (MeSiCl
₃), and trimethylsilyl chloride (Me
₃SiCl) are all produced by direct process. 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 Me
₃SiCl is the main silylating agent. One classic method called the Flood reaction for the synthesis of this compound class is by heating hexaalkyldisiloxanes R
₃SiOSiR
₃ with concentrated sulfuric acid and a sodium halide.^[23]

Silyl hydrides

Main article: Hydrosilane

Tris(trimethylsilyl)silane is a well-investigated hydrosilane.^[24]

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 Et
₃SiH. Phenylsilane is PhSiH
₃. The parent compound SiH
₄ is called silane.

Silenes

Organosilicon compounds, unlike their carbon counterparts, do not have a rich double bond chemistry.^[25] 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.^[26] The first stable (kinetically shielded) silene was reported in 1981 by Brook.^[27][28]

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.^[29]

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.^[30][31] 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.

Pentacoordinated silicon

See also: Hypervalent molecule § Pentacoordinated 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:^[32]

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 a Si-C bond by fluoride:

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

Various reactions

In general, almost any silicon-heteroatom bond is water-sensitive, and will spontaneously hydrolyze.^[33] Unstrained silicon-carbon bonds, however, are very strong, and cleave only in a small number of extreme conditions. Strong acids will protodesilate arylsilanes and, in the presence of a Lewis acid catalyst, alkylsilanes. Most nucleophiles are too weak to displace carbon from silicon: the exceptions are fluoride ions and alkoxides, although the latter often deprotonate the organosilane to a silicon ylide instead.^[34]

As a covalent hydride source, hydrosilanes are good reductants.

Certain allyl silanes can be prepared from allylic esters such as 1 and monosilylcopper compounds, which are formed in situ by the reaction of the disilylzinc compound 2, with Copper Iodide, in:^[35][36]

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.

Unsaturated silanes like the above are susceptible to electrophilic substitution.

Environmental effects

Organosilicon compounds affect bee (and other insect) immune expression, making them more susceptible to viral infection.^[13][37]

See also

• Compounds of carbon with period 3 elements: organoaluminum compounds, organophosphorus compounds, organosulfur compounds
• Compounds of carbon with other group 14 elements: organogermanium compounds, organotin compounds, organolead compounds
• Silylenes, the carbene counterparts
• Silylenoids, the carbenoid counterparts
• Decamethylsilicocene

References

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36. 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 or reductive elimination step
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External links

• Magnus Walter's Selected Aspects of Organosilicon Chemistry
• Silicon in organic synthesis
• S. Marsden (Editor): Contemporary organosilicon chemistry. Thematic Series in the Open Access Beilstein Journal of Organic Chemistry.