An Air-Stable Heterobimetallic Si2M2 Tetrahedral Cluster

Gizem Dübek; Franziska Hanusch; Dominik Munz; Shigeyoshi Inoue

doi:10.1002/anie.201916116

An Air-Stable Heterobimetallic Si₂M₂ Tetrahedral Cluster

Gizem Dübek, Franziska Hanusch, Dominik Munz, Shigeyoshi Inoue

Chair of Silicon Chemistry

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

Air- and moisture-stable heterobimetallic tetrahedral clusters [Cp(CO)₂MSiR]₂ (M=Mo or W; R=SitBu₃) were isolated from the reaction of N-heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)₂M=Si(SitBu₃)NHC with a mild Lewis acid (BPh₃). Alternatively, treatment of the NHC-stabilized silylidene complex Cp(CO)₂W=Si(SitBu₃)NHC with stronger Lewis acids such as AlCl₃ or B(C₆F₅)₃ resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four-membered ring is due to steric bulk.

Original language	English
Pages (from-to)	5823-5829
Number of pages	7
Journal	Angewandte Chemie International Edition in English
Volume	59
Issue number	14
DOIs	https://doi.org/10.1002/anie.201916116
State	Published - 27 Mar 2020

Keywords

cluster compounds
silicon
silylidenes
silylidynes
tetrahedranes

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title = "An Air-Stable Heterobimetallic Si2M2 Tetrahedral Cluster",

abstract = "Air- and moisture-stable heterobimetallic tetrahedral clusters [Cp(CO)2MSiR]2 (M=Mo or W; R=SitBu3) were isolated from the reaction of N-heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)2M=Si(SitBu3)NHC with a mild Lewis acid (BPh3). Alternatively, treatment of the NHC-stabilized silylidene complex Cp(CO)2W=Si(SitBu3)NHC with stronger Lewis acids such as AlCl3 or B(C6F5)3 resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four-membered ring is due to steric bulk.",

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author = "Gizem D{\"u}bek and Franziska Hanusch and Dominik Munz and Shigeyoshi Inoue",

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T1 - An Air-Stable Heterobimetallic Si2M2 Tetrahedral Cluster

AU - Dübek, Gizem

AU - Hanusch, Franziska

AU - Munz, Dominik

AU - Inoue, Shigeyoshi

PY - 2020/3/27

Y1 - 2020/3/27

N2 - Air- and moisture-stable heterobimetallic tetrahedral clusters [Cp(CO)2MSiR]2 (M=Mo or W; R=SitBu3) were isolated from the reaction of N-heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)2M=Si(SitBu3)NHC with a mild Lewis acid (BPh3). Alternatively, treatment of the NHC-stabilized silylidene complex Cp(CO)2W=Si(SitBu3)NHC with stronger Lewis acids such as AlCl3 or B(C6F5)3 resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four-membered ring is due to steric bulk.

AB - Air- and moisture-stable heterobimetallic tetrahedral clusters [Cp(CO)2MSiR]2 (M=Mo or W; R=SitBu3) were isolated from the reaction of N-heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)2M=Si(SitBu3)NHC with a mild Lewis acid (BPh3). Alternatively, treatment of the NHC-stabilized silylidene complex Cp(CO)2W=Si(SitBu3)NHC with stronger Lewis acids such as AlCl3 or B(C6F5)3 resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four-membered ring is due to steric bulk.

KW - cluster compounds

KW - silicon

KW - silylidenes

KW - silylidynes

KW - tetrahedranes

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JO - Angewandte Chemie International Edition in English

JF - Angewandte Chemie International Edition in English

IS - 14

ER -

An Air-Stable Heterobimetallic Si₂M₂ Tetrahedral Cluster

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