Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
J Am Chem Soc. 2012 Apr 18;134(15):6504-7. doi: 10.1021/ja301091v. Epub 2012 Apr 6.
The synthesis and characterization of a stable, acyclic two-coordinate silylene, Si(SAr(Me(6)))(2) [Ar(Me(6)) = C(6)H(3)-2,6(C(6)H(2)-2,4,6-Me(3))(2)], by reduction of Br(2)Si(SAr(Me(6)))(2) with a magnesium(I) reductant is described. It features a V-shaped silicon coordination with a S-Si-S angle of 90.52(2)° and an average Si-S distance of 2.158(3) Å. Although it reacts readily with an alkyl halide, it does not react with hydrogen under ambient conditions, probably as a result of the ca. 4.3 eV energy difference between the frontier silicon lone pair and 3p orbitals.
描述了通过镁(I)还原剂还原 Br2Si(SAr(Me6))2合成和表征稳定的非循环二配位硅烯 Si(SAr(Me6))2(Ar(Me6) = C6H3-2,6(C6H2-2,4,6-Me3)2)。它具有 V 形硅配位,S-Si-S 角为 90.52(2)°,平均 Si-S 距离为 2.158(3)Å。尽管它容易与卤代烃反应,但在环境条件下不会与氢反应,这可能是由于前沿硅孤对和 3p 轨道之间约 4.3 eV 的能量差造成的。