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

Pure And Applied Chemistry

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

30 Citations (Scopus)

35 Downloads (Pure)

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-Me ₃C ₆H ₂) ₂C ₆H ₃; NHC= IMe ₄=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO ₂ 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
Publication status	Published - 9 Sept 2021

Keywords

CO conversion
DFT
N-heterocyclic carbenes
catalysis
cations
germanium

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@article{85f1c1980f464067871ce4088f1773ee,

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−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-Me 3C 6H 2) 2C 6H 3; NHC= IMe 4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO 2 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",

year = "2021",

month = sep,

day = "9",

doi = "10.1002/chem.202102233",

language = "English",

volume = "27",

pages = "13072--13078",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

number = "51",

}

TY - JOUR

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−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-Me 3C 6H 2) 2C 6H 3; NHC= IMe 4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO 2 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−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-Me 3C 6H 2) 2C 6H 3; NHC= IMe 4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO 2 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

U2 - 10.1002/chem.202102233

DO - 10.1002/chem.202102233

M3 - Article

SN - 0947-6539

VL - 27

SP - 13072

EP - 13078

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 51

ER -

Germyliumylidene: a versatile low valent group 14 catalyst

Abstract

Keywords

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