Silylene

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generic silylene
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Silylene is a chemical compound with the formula SiR2 (R = H). It is the silicon analog of carbene. Silylenes decomposes rapidly when condensed.

Silylenes are formal derivatives of silylene with its hydrogens replaced by other substituents.[2] Most examples feature amido (NR2) or organyl groups.[3][4]

Silylenes have been proposed as reactive intermediates. They are carbene analogs.[5]

Synthesis and properties

Silylenes have been generated by thermolysis or photolysis of polysilanes, by silicon atom reactions (insertion, addition or abstraction), by pyrolysis of silanes, or by reduction of 1,1-dihalosilane. It has long been assumed that the conversion of metallic Si to tetravalent silicon compounds proceeds via silylene intermediates:

Si + Cl2 → SiCl2
SiCl2 + Cl2 → SiCl4

Similar considerations apply to the direct process, the reaction of methyl chloride and bulk silicon.

Early observations of silylenes involved generation of dimethylsilylene by dechlorination of dimethyldichlorosilane:[6]

SiCl2(CH3)2 + 2 K → Si(CH3)2 + 2 KCl

The formation of dimethylsilylene was demonstrated by conducting the dechlorination in the presence of trimethylsilane: the trapped product being pentamethyldisilane:

Si(CH3)2 + HSi(CH3)3 → (CH3)2Si(H)−Si(CH3)3

A room-temperature isolable N-heterocyclic silylene is Template:Chem name:[7]

File:DenkSiR2.png
Synthesis of an isolable silylene.

The α-amido centers stabilize silylenes by π-donation. The dehalogenation of diorganosilicon dihalides is a widely exploited.[8]

Related reactions

File:Decamethylsilicocene.png
Decamethylsilicocene is an example of a silylene.[3]

In one study diphenylsilylene is generated by flash photolysis of a trisilane:[9]

Diphenylsilylene

In this reaction diphenylsilylene is extruded from the trisila ring. The silylene can be observed with UV spectroscopy at 520 nm and is short-lived with a chemical half-life of two microseconds. Added methanol acts as a chemical trap with a second order rate constant of Script error: No such module "val". which is close to diffusion control.

See also

References

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