Chemistry of functionalized silylenes
Chemistry of functionalized silylenes
复制标题
DOI：
10.1039/c1sc00757b
复制
发表时间：
2012-01-01
期刊：
影响因子：
8.4
通讯作者：
Roesky, Herbert W.
中科院分区：
文献类型：
--
作者：
Sen, Sakya S.;Khan, Shabana;Roesky, Herbert W.
近年来，由于高收率地获得稳定的单体氯代甲硅烯，有机硅化学取得了重要进展（LSiCl，L = PhC（NtBu）（2））和N-杂环卡宾（NHC）稳定的二氯甲硅烷基（（LSiCl 2）-Si-1，L-1 1，3-bis（2，6-iPr（2）C（6）H（3））咪唑-2-亚基）通过脱氯化氢技术使用强碱如N-杂环卡宾或LiN（SiMe 3）（2）作为HCl清除剂。官能化的亚甲硅烷基的化学性质与先前报道的二配位亚甲硅烷基明显不同。他们的实用性，作为药物是有据可查的，这铺平了道路，为几个引人注目的化合物，如。G.单硅氧杂环丙烷、CSi 2 P衍生物、CSi 3 P阳离子、具有二配位Si原子的硅异腈（Si 2 N2）二聚体等。这项研究还揭示了这些官能化的亚甲硅烷基擅长活化磷，并且连接到硅（II）中心的α位上的官能团在确定最终产物方面发挥着关键作用。P-4与LSiCl反应得到两性离子Si 2 P2环，而与LSiN（SiMe 3）（2）反应得到无环Si 2 P4衍生物。该领域的另一个最新成就是成功地分离出了二硅炔的价态异构体，称为互连双亚硅烷基。这一观点描绘了官能化硅烯的化学，这将引起极大的关注，走向有机硅化学的进一步发展。
Recent years have witnessed important developments in organosilicon chemistry, courtesy to the high yield access of stable monomeric chlorosilylene (LSiCl, L = PhC(NtBu)(2)) and N-heterocyclic carbene (NHC) stabilized dichlorosilylene ((LSiCl2)-Si-1, L-1 1,3-bis(2,6-iPr(2)C(6)H(3))imidazol-2-ylidene) by dehydrochlorination technique using strong bases such as N-heterocyclic carbenes or LiN(SiMe3)(2) as HCl scavenger. The chemistry of functionalized silylenes is markedly different from the previously reported dicoordinate silylenes. Their utility as synthons is well documented which paves the way for several striking compounds, e. g. monosilaoxiranes, CSi2P derivative, CSi3P cation, a dimer of silaisonitrile (Si2N2) with dicoordinate Si atoms etc. This study also unravels that these functionalized silylenes are proficient at activating phosphorus, and the functional group attached to the alpha-position of the silicon(II) centre plays a key role to determine the final product. The reaction of P-4 with LSiCl affords a zwitterionic Si2P2 ring, while with LSiN(SiMe3)(2) it gives an acyclic Si2P4 derivative. Another recent achievement in this field is the successful isolation of a valence isomer of disilyne known as the inter-connected bis-silylene. This perspective portrays the chemistry of functionalized silylenes which will attract great attention, heading for the further development of organosilicon chemistry.