Reactivity of heavier vinyl anions [(CH3)2-rfeti=E'(CH3)]- (E, E' = C, Si, Ge) toward carbon monoxide: A computational study

Yıldız, Cem BurakScheschkewitz, David13.07.20192019-07-1613.07.20192019-07-1620170276-7333https://dx.doi.org/10.1021/acs.organomet.7b00327https://hdl.handle.net/20.500.12451/2287The structures of heavier vinyl anions [(CH3)2E=E'(CH3)]- (E, E' = C, Si, Ge) and their abilities to activate carbon monoxide were investigated by DFT. Particularly, heteronuclear species exhibit a strong influence of the position of the heavier of the two group 14 elements (E or E') with strongly differing singlet-triplet gaps as a measure of tetrylene character. The reactions of CSi and CGe (E' = Si, Ge) with CO proceed in a concerted manner via [1 + 2] or [2 + 2] cycloadditions to a variety of potential products, whereas those of positional isomers as well as digerma and sila-germa analogues occur in a stepwise fashion. The three-membered rings derived from tetrylene-like vinyl anions (E' = Si, Ge and E = C) are dominated by keto resonance structures, while an enol structure is observed for the product obtained from SiC. Allene-like isomers could only be optimized in case of E = Si, Ge. © 2017 American Chemical Society.eninfo:eu-repo/semantics/closedAccessReactivity of heavier vinyl anions [(CH3)2-rfeti=E'(CH3)]- (E, E' = C, Si, Ge) toward carbon monoxide: A computational studyArticle36163035304210.1021/acs.organomet.7b00327Q2N/A