Diazomethane addition to sumanene as a subfullerene structure: A theoretical mechanistic study

Abstract

In present study, kinetics and reaction mechanism of diazomethane and sumanene in gas phase were studied using quantum calculations at B3LYP/6-311+G(d,p) level of theory. Functionalization of the sumanene by this reaction was investigated in proposed fourteen pathways for different kinds of CC bond. Vibrational frequencies analysis and intrinsic reaction coordinate (IRC) calculations were carried out and the rate constants for all paths were calculated by using canonical transition state theory (CTST). The best and the worst paths and dominant products for this reaction were determined. Stability of the intermediates, transition sates and products was discussed. Results showed that in the first step of CH2N2 addition to sumanene and formation of corresponding transition state, hub position has the least and rim position has the most barrier energy. Also, for all types of CC bond, sumanene with a CH2 group as a bridge was formed and conversion of a sumanene hexagon to heptagon happened for all positions except spoke. Generally, diazomethane can add a CH2 group in the carbon chain, insert CH2 group as a bridge or add a CH3 group to the structure.