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

Professur für Siliciumchemie

Publikation: Beitrag in Fachzeitschrift › Artikel › Begutachtung

8 Zitate (Scopus)

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.

Originalsprache	Englisch
Seiten (von - bis)	5823-5829
Seitenumfang	7
Fachzeitschrift	Angewandte Chemie International Edition in English
Jahrgang	59
Ausgabenummer	14
DOIs	https://doi.org/10.1002/anie.201916116
Publikationsstatus	Veröffentlicht - 27 März 2020

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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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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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