一种σ供体镍稳定的亚硅烯离子的合成、表征及反应活性
Synthesis, Characterization and Reactivity of a σ-Donating Ni -Stabilized Silyliumylidene Ion.
作者信息
Takahashi Shintaro, Frutos María, Baceiredo Antoine, Madec David, Saffon-Merceron Nathalie, Branchadell Vicenç, Kato Tsuyoshi
机构信息
Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France) (Equipe-ECOIH.
Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
出版信息
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202208202. doi: 10.1002/anie.202208202. Epub 2022 Aug 8.
The synthesis of a silyliumylidene cation complex 2 stabilized by a Ni -based donating ligand is reported. Experimental and theoretical studies demonstrate that the highly electrophilic Si center is stabilized by a dative Ni→Si σ-interaction and π-donations from the amino- and Ni-moieties. Due to the energetically close frontier orbitals localized on the Si and Ni atoms, complex 2 presents a competitive reactivity at Si and Ni sites.
报道了一种由镍基给体配体稳定的硅亚烷基阳离子配合物2的合成。实验和理论研究表明，高亲电的硅中心通过Ni→Si的配位σ相互作用以及氨基和镍部分的π电子给予作用得以稳定。由于硅和镍原子上能量相近的前沿轨道，配合物2在硅和镍位点表现出竞争性反应活性。
Zotero 插件