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A Stable N-Hetero-Rh-Metallacyclic Silylene.
Takahashi, Shintaro; Bellan, Ekaterina; Baceiredo, Antoine; Saffon-Merceron, Nathalie; Massou, Stéphane; Nakata, Norio; Hashizume, Daisuke; Branchadell, Vicenç; Kato, Tsuyoshi.
Afiliação
  • Takahashi S; Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
  • Bellan E; Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
  • Baceiredo A; Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
  • Saffon-Merceron N; Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
  • Massou S; Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
  • Nakata N; Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
  • Hashizume D; RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
  • Branchadell V; Departament de Química, Universitat Autònoma de Barcelona, 08193, Bellaterra, Spain.
  • Kato T; Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
Angew Chem Int Ed Engl ; 58(30): 10310-10314, 2019 Jul 22.
Article em En | MEDLINE | ID: mdl-31132319
ABSTRACT
A cyclic (amino)metal-substituted dicoordinated silylene derivative has been synthesized and fully characterized. Of particular interest is that the N-hetero-RhI -metallacyclic silylene exhibits a distorted tetrahedral geometry around the rhodium atom and a considerably shortened Si-Rh bond (2.138 Å) compared to classical Si-Rh single bonds (ca. 2.30-2.35 Å). A theoretical investigation reveals that the geometrical deviation around the rhodium center from the classical square-planar to a tetrahedral geometry increases the π-donating and σ-accepting character of the rhodium atom, thereby efficiently stabilizing the silylene moiety.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article