2021
DOI: 10.1002/chem.202102233
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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 GeÀ C NHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHCstabilized germyliumylidene [ Mes TerGe(NHC) 2 ]Cl (1), ( Mes Ter = 2,6-(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 ; NHC = IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene) cata… Show more

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Cited by 34 publications
(41 citation statements)
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“…As examined from the above stoichiometric reactions and reported Ge TMSCN addition in carbonyls [8,14] We suggest a plausible mechanism for Ge hydride 2 catalyzed the cyanosilylation of ketones in Scheme 8. At the start of the catalytic cycle, trimethylsilyl cyanide coordinate with the active germanium hydride (2) to afford labile Lewis acid-base adduct (Int A1).…”
Section: Catalytic Cycle For Ketone Cyanosilylationmentioning
confidence: 67%
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“…As examined from the above stoichiometric reactions and reported Ge TMSCN addition in carbonyls [8,14] We suggest a plausible mechanism for Ge hydride 2 catalyzed the cyanosilylation of ketones in Scheme 8. At the start of the catalytic cycle, trimethylsilyl cyanide coordinate with the active germanium hydride (2) to afford labile Lewis acid-base adduct (Int A1).…”
Section: Catalytic Cycle For Ketone Cyanosilylationmentioning
confidence: 67%
“…For cyanosilylation of acetophenone, CBG germaniumÀ hydride (2) displayed a TON (33.3) and the corresponding TOF (4.2 h À 1 ) relative to recently reported NHC stabilized germanium cation [14] ((H) TON = 100 and TOF = 7 h À 1 ) (Table S2 of ESI). The TMSCN addition in acetophenone was performed under a lower catalyst amount at rt; however, the [d] no cat.…”
Section: Cyanosilylation Of Ketone With Trimethylsilyl Cyanidementioning
confidence: 76%
“…interactions and organic transformations. Recently, there have been significant achievements in this emerging field of ligand supported E(II) cations in metal-ligand cooperativity, [17] as versatile catalysts [18] etc. In this personal account, we will rigorously analyze our efforts in this field as well as discuss the recent important developments by others in relevance to our research focus.…”
Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning
confidence: 99%
“…In this direction, Inoue et al established the bis-NHCstabilized germyliumylidene as a versatile catalyst due to its ambiphilic nature. [18] Hydrosilylation of CO 2 and N-methylation of amines using CO 2 as a C1 source have been achieved based on the Lewis basic nature of bis-NHC stabilized germyliumylidene. On the other hand, the electrophilic nature arising from the Ge-C NHC σ* orbital has been utilized in the hydroboration and cyanosilylation of carbonyls.…”
Section: B Role Of Ligand Stabilized E(ii) Cations (E = Ge Sn) In Org...mentioning
confidence: 99%
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