Germyliumylidene : a versatile low valent group 14 catalyst

Sarkar, Debotra and Dutta, Sayan and Weetman, Catherine and Schubert, Emeric and Koley, Debasis and Inoue, Shigeyoshi (2021) Germyliumylidene : a versatile low valent group 14 catalyst. Chemistry - A European Journal, 27 (51). pp. 13072-13078. ISSN 0947-6539 (https://doi.org/10.1002/chem.202102233)

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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.

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