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A Stable N‐Hetero ‐Rh ‐Metallacyclic Silylene
Author(s) -
Takahashi Shintaro,
Bellan Ekaterina,
Baceiredo Antoine,
SaffonMerceron Nathalie,
Massou Stéphane,
Nakata Norio,
Hashizume Daisuke,
Branchadell Vicenç,
Kato Tsuyoshi
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904594
Subject(s) - silylene , rhodium , moiety , chemistry , crystallography , derivative (finance) , atom (system on chip) , tetrahedron , stereochemistry , metal , catalysis , silicon , organic chemistry , computer science , financial economics , economics , embedded system
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.