A DFT insight into the structure and electronic characteristics of group 14 bis-atranes and their analoges

Abstract

The competing multicenter bonding mechanisms (3c-4e and 5c-6e flip-flop effect), defining the structures and stability of the symmetric Group 14 bis-atranes RX(YCH2CH2)3N(CH2CH2Y)3XR and their analogs RX(YCH2CH2)3P(CH2CH2Y)3XR were investigated based on the density functional theory B3LYP/QZVP and M06/def2TZVP calculations and the AIM analysis of electronic distribution in molecules of the hypervalent compounds. Flip-flop effect was detected in bis-atranes (for X=Sn, Pb) and for all X centers in the case of phosphorus-containing analogs. Barriers do not exceed 1 kcal/mol for bis-atranes and do not exceed 14 kcal/mol for systems with phosphorus.