硅烯[PhC(NtBu)](CMe)Si的反应性研究——与[M(COD)Cl]（M = Rh(i)，Ir(i)）、S、Se、Te和BH的反应

Reactivity studies of silylene [PhC(NtBu)](CMe)Si - reactions with [M(COD)Cl] (M = Rh(i), Ir(i)), S, Se, Te, and BH.

作者信息

Kaufmann Sebastian, Schäfer Sebastian, Gamer Michael T, Roesky Peter W

机构信息

Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe, Germany.

出版信息

Dalton Trans. 2017 Jul 11;46(27):8861-8867. doi: 10.1039/c7dt00483d.

DOI:10.1039/c7dt00483d

PMID:28489092

Abstract

The reactivity of recently introduced N-heterocyclic silylene PhC(NtBu)Si was evaluated. Three different reaction pathways were studied: (1) coordination to a Lewis acid, (2) oxidation by chalcogenides, and (3) coordination to transition metal complexes. The reaction of the silylene with BH led to the adduct PhC(NtBu)Si(BH). Oxidation with the elemental chalcogens sulphur, selenium, and tellurium resulted in the corresponding silicon(iv)-chalcogenide compounds PhC(NtBu)SiS, PhC(NtBu)SiSe and PhC(NtBu)SiTe. Treatment of the silylene with dimeric group 9 transition metal complexes [Ir(COD)Cl] and [Rh(COD)Cl] gave square planar coordinated transition metal silylene complexes [{PhC(NtBu)}(CMe)Si-Rh(COD)(Cl)] and [{PhC(NtBu)}(CMe)Si-Ir(COD)(Cl)].

摘要

对最近引入的N-杂环硅烯PhC(NtBu)Si的反应活性进行了评估。研究了三种不同的反应途径：(1)与路易斯酸配位，(2)被硫族元素氧化，以及(3)与过渡金属配合物配位。硅烯与BH反应生成加合物PhC(NtBu)Si(BH)。与元素硫族元素硫、硒和碲发生氧化反应，生成相应的硅(IV)-硫族化合物PhC(NtBu)SiS、PhC(NtBu)SiSe和PhC(NtBu)SiTe。用二聚体第9族过渡金属配合物[Ir(COD)Cl]和[Rh(COD)Cl]处理硅烯，得到平面正方形配位的过渡金属硅烯配合物[{PhC(NtBu)}(CMe)Si-Rh(COD)(Cl)]和[{PhC(NtBu)}(CMe)Si-Ir(COD)(Cl)]。