ИСТИНА

Sigmatropic 1,2-shift of -substituents, which transforms the carbene or carbenoid into alkene, is a fundamentally important process and has received adequate attention in both experimental and theoretical studies. However, their main focus was on 1,2-H and 1,2-C migrations, while 1,2-shifts of RnE groups formed by elements other than hydrogen and carbon is less explored. As far as we know, the presented study gives the first systematic comparison of the migrational ability of groups formed by different elements in carbenes or carbenoids. The RnE- 1,2-shift is studied on the model of carbenoid anions [RnECF2CFCl]- derived from the addition of [RnE]- nucleophile to CF2=CFCl using DFT calculations (PBE/TZ2p, PRIRODA suite [1]), both for free anions and their Na+ and [NMe4]+ salts.