A Stable N-Hetero-Rh-Metallacyclic Silylene

Shintaro Takahashi; Ekaterina Bellan; Antoine Baceiredo; Nathalie Saffon-Merceron; Stéphane Massou; Norio Nakata; Daisuke Hashizume; Vicenç Branchadell; Tsuyoshi Kato

doi:10.1002/anie.201904594

A Stable N-Hetero-Rh-Metallacyclic Silylene

Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10310-10314. doi: 10.1002/anie.201904594. Epub 2019 Jun 24.

Authors

Shintaro Takahashi¹, Ekaterina Bellan², Antoine Baceiredo², Nathalie Saffon-Merceron³, Stéphane Massou³, Norio Nakata¹, Daisuke Hashizume⁴, Vicenç Branchadell⁵, Tsuyoshi Kato²

Affiliations

¹ Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
² Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
³ Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062, Toulouse, France.
⁴ RIKEN Center for Emergent Matter Science (CEMS), 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
⁵ Departament de Química, Universitat Autònoma de Barcelona, 08193, Bellaterra, Spain.

PMID: 31132319
DOI: 10.1002/anie.201904594

Abstract

A cyclic (amino)metal-substituted dicoordinated silylene derivative has been synthesized and fully characterized. Of particular interest is that the N-hetero-Rh^I -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.

Keywords: N-heterocyclic silylenes; metallacycles; rhodium; silylenes; structure elucidation.

Abstract

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