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路易斯酸辅助的 N-杂环氯代硅烯反应形成供体质稳的四硅环丁二烯二阳离子。

Formation of a donor-stabilized tetrasilacyclobutadiene dication by a Lewis acid assisted reaction of an N-heterocyclic chloro silylene.

机构信息

Institute of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17, Juni 135, Sekr. C2, D-10623 Berlin, Germany.

出版信息

J Am Chem Soc. 2011 Jun 8;133(22):8514-7. doi: 10.1021/ja2033475. Epub 2011 May 11.

Abstract

The first donor-stabilized tetrasilacyclobutadiene dication species has been synthesized and fully characterized. Its unexpected formation occurs by the Lewis acid assisted reaction of the N-heterocyclic chloro silylene [L(Si:)Cl] (L = PhC(NtBu)(2); amidinate) with CpZrCl(3) (Cp = pentamethylcyclopentadienyl) in the molar ratio of 3:2. Remarkably, the four-membered Si(4) core consists of two N-donor stabilized silylium subunits and two silylene-like moieties. The dicationic charge is somewhat delocalized on the Si(4) core, which is supported by DFT calculations.

摘要

首例供体稳定的四硅环丁二烯二阳离子物种已被合成并进行了全面表征。其通过路易斯酸辅助的 N-杂环氯代硅亚胺 [L(Si:)Cl](L = PhC(NtBu)(2);酰胺基)与 CpZrCl(3)(Cp = 五甲基环戊二烯基)在摩尔比为 3:2 的条件下反应而意外形成。值得注意的是,四元 Si(4)核由两个 N-供体稳定的硅鎓亚基和两个类似硅烯的部分组成。阳离子电荷在 Si(4)核上有些离域,这得到了 DFT 计算的支持。

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