Silylene

Last updated
generic silylene
Silylene.svg
Simplest silylene has R=Hydrogen
Silylene-3D-vdW.png
Names
IUPAC name
Silylene
Systematic IUPAC name
Silylidene [1]
Other names
Hydrogen silicide(−II)
Silicene
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/H2Si/h1H2 Yes check.svgY
    Key: XMIJDTGORVPYLW-UHFFFAOYSA-N Yes check.svgY
  • [SiH2]
Properties
H2Si
Molar mass 30.101 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Silylene is a chemical compound with the formula SiR2. It is the silicon analog of carbene. Silylene rapidly when condensed.

Contents

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 N,N′-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene: [7]

Synthesis of an isolable silylene. 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]

Decamethylsilicocene is an example of a silylene. Decamethylsilicocene.png
Decamethylsilicocene is an example of a silylene.

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

Diphenylsilylene.png

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 1.3×1010 mol−1 s−1 which is close to diffusion control.

See also

References

  1. ↑ IUPAC Chemical Nomenclature and Structure Representation Division (2013). "P-71.2.2.1". In Favre, Henri A.; Powell, Warren H. (eds.). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. IUPAC–RSC. ISBN   978-0-85404-182-4.
  2. ↑ Mizuhata, Yoshiyuki; Sasamori, Takahiro; Tokitoh, Norihiro (2009). "Stable Heavier Carbene Analogues". Chemical Reviews. 109 (8): 3479–3511. doi:10.1021/cr900093s. PMID   19630390.
  3. 1 2 Nagendran, Selvarajan; Roesky, Herbert W. (2008). "The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)". Organometallics. 27 (4): 457–492. doi:10.1021/om7007869.
  4. ↑ Haaf, Michael; Schmedake, Thomas A.; West, Robert (2000). "Stable Silylenes". Accounts of Chemical Research. 33 (10): 704–714. doi:10.1021/ar950192g. PMID   11041835.
  5. ↑ Gaspar, Peter; West, R. (1998). "Silylenes". The Chemistry of Organic Silicon Compounds. The Chemistry of Functional Groups. Vol. 2. pp. 2463–2568. doi:10.1002/0470857250.ch43. ISBN   0471967572.
  6. ↑ Skell, P. S.; Goldstein, E. J. (1964). "Dimethylsilene: CH3SiCH3". Journal of the American Chemical Society. 86 (7): 1442–1443. doi:10.1021/ja01061a040.
  7. ↑ Denk, Michael; Lennon, Robert; Hayashi, Randy; West, Robert; Belyakov, Alexander V.; Verne, Hans P.; Haaland, Arne; Wagner, Matthias; Metzler, Nils (1994). "Synthesis and Structure of a Stable Silylene". Journal of the American Chemical Society. 116 (6): 2691–2692. doi:10.1021/ja00085a088.
  8. ↑ Driess, Matthias; Yao, Shenglai; Brym, Markus; Van Wüllen, Christoph; Lentz, Dieter (2006). "A New Type of N-Heterocyclic Silylene with Ambivalent Reactivity". Journal of the American Chemical Society. 128 (30): 9628–9629. doi:10.1021/ja062928i. PMID   16866506.
  9. ↑ Moiseev, Andrey G.; Leigh, William J. (2006). "Diphenylsilylene". Journal of the American Chemical Society. 128 (45): 14442–14443. doi:10.1021/ja0653223. PMID   17090011.
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