Reactivity of germanones: far removed from ketones – a computational study

• DOI: 10.1039/c3ra44352c
• Publication Date: 2013-09-18T15:10:27Z
• Authors: A. K. Jissy; Sanjay K. Meena; Ayan Datta
• Keywords: Reactivity; Natural bond orbital; Nucleophilic Addition

The recently isolated heavy ketone (X2EO; E = Ge) shows interesting reactivity towards simple addition reactions that are unknown for the organic (EC) ketones. Density Functional Theory (DFT) calculations elucidate role of central atom and substituent effects on acetone, carbon dioxide water to formaldehyde, 2,4-dimethyl-3-pentanone, diphenyl their heavier (Si, analogs. NBO analysis reveals a large charge separation analogs, thereby increasing reactivity. activation barriers reduced by as much ∼30.0 40.0 kcal mol−1 nucleophilic ketones (E Si compared those an ketone. Comparably lower stability reactants higher transition state lowers Apart from smaller barrier, which unfavorable favored 20–40 silicon germanium counterparts. Calculations predict similar must be feasible silanones (X2SiO) well.