Germyliumylidene: A Versatile Low Valent Group 14 Catalyst

Debotra Sarkar; Sayan Dutta; Catherine Weetman; Emeric Schubert; Debasis Koley; Shigeyoshi Inoue

doi:10.1002/chem.202102233

Germyliumylidene: A Versatile Low Valent Group 14 Catalyst

Debotra Sarkar, Sayan Dutta, Catherine Weetman, Emeric Schubert, Debasis Koley, Shigeyoshi Inoue

Chair of Silicon Chemistry

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

34 Scopus citations

Abstract

Bis-NHC stabilized germyliumylidenes [RGe(NHC)₂]⁺ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge−C^NHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [^MesTerGe(NHC)₂]Cl (1), (^MesTer=2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃; NHC= IMe₄=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO₂ with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.

Original language	English
Pages (from-to)	13072-13078
Number of pages	7
Journal	Chemistry - A European Journal
Volume	27
Issue number	51
DOIs	https://doi.org/10.1002/chem.202102233
State	Published - 9 Sep 2021

Keywords

CO conversion
DFT
N-heterocyclic carbenes
catalysis
cations
germanium

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title = "Germyliumylidene: A Versatile Low Valent Group 14 Catalyst",

abstract = "Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge−CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.",

keywords = "CO conversion, DFT, N-heterocyclic carbenes, catalysis, cations, germanium",

author = "Debotra Sarkar and Sayan Dutta and Catherine Weetman and Emeric Schubert and Debasis Koley and Shigeyoshi Inoue",

note = "Publisher Copyright: {\textcopyright} 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH",

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T1 - Germyliumylidene

T2 - A Versatile Low Valent Group 14 Catalyst

AU - Sarkar, Debotra

AU - Dutta, Sayan

AU - Weetman, Catherine

AU - Schubert, Emeric

AU - Koley, Debasis

AU - Inoue, Shigeyoshi

PY - 2021/9/9

Y1 - 2021/9/9

N2 - Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge−CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.

AB - Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge−CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.

KW - CO conversion

KW - DFT

KW - N-heterocyclic carbenes

KW - catalysis

KW - cations

KW - germanium

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JO - Chemistry - A European Journal

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ER -

Germyliumylidene: A Versatile Low Valent Group 14 Catalyst

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