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

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

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18 Citations (Scopus)

Abstract

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.

Original language	English
Pages (from-to)	10310-10314
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	30
DOIs	https://doi.org/10.1002/anie.201904594
Publication status	Published - 22 Jul 2019

Keywords

metallacycles
N-heterocyclic silylenes
rhodium
silylenes
structure elucidation

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10.1002/anie.201904594

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title = "A Stable N-Hetero-Rh-Metallacyclic Silylene",

abstract = "{\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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 {\AA}) compared to classical Si−Rh single bonds (ca. 2.30–2.35 {\AA}). 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 = "metallacycles, N-heterocyclic silylenes, rhodium, silylenes, structure elucidation",

author = "Shintaro Takahashi and Ekaterina Bellan and Antoine Baceiredo and Nathalie Saffon-Merceron and St{\'e}phane Massou and Norio Nakata and Daisuke Hashizume and Vicen{\c c} Branchadell and Tsuyoshi Kato",

note = "{\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2019",

month = jul,

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doi = "10.1002/anie.201904594",

language = "English",

volume = "58",

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journal = "Angewandte Chemie - International Edition",

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T1 - A Stable N-Hetero-Rh-Metallacyclic Silylene

AU - Takahashi, Shintaro

AU - Bellan, Ekaterina

AU - Baceiredo, Antoine

AU - Saffon-Merceron, Nathalie

AU - Massou, Stéphane

AU - Nakata, Norio

AU - Hashizume, Daisuke

AU - Branchadell, Vicenç

AU - Kato, Tsuyoshi

PY - 2019/7/22

Y1 - 2019/7/22

N2 - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.

AB - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 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.

KW - metallacycles

KW - N-heterocyclic silylenes

KW - rhodium

KW - silylenes

KW - structure elucidation

UR - http://www.mendeley.com/research/stable-nheterorhmetallacyclic-silylene

U2 - 10.1002/anie.201904594

DO - 10.1002/anie.201904594

M3 - Article

C2 - 31132319

SN - 1433-7851

VL - 58

SP - 10310

EP - 10314

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 30

ER -

A Stable N-Hetero-Rh-Metallacyclic Silylene

Abstract

Keywords

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