Entropic corrections for the evaluation of the catalytic activity in the Al(iii) catalysed formation of cyclic carbonates from CO2 and epoxides A data set of input files and computational results is available in the ioChem-BD repository and can be accessed via; http://dx.doi.org/10.19061/iochem-bd-1-110.Electronic supplementary information (ESI) available: A detailed description of the methods used for including entropic corrections in solution. See DOI: 10.1039/c9cy01285k

摘要

The reaction mechanism for formation of cyclic carbonates from CO2 and 1,2-epoxyhexane catalyzed by an [Al(amino-triphenolate)]/NBu4I binary system has been investigated by using density functional theory (DFT) based methods. A monometallic mechanism is proposed and the main steps of the reaction are described in detail. The energetic span model (delta E) was used to theoretically determine the turnover frequencies (TOFs) of the catalytic cycle and to evaluate the efficiency of the aluminum complex in mediating the CO2 addition reaction. Our findings indicate that entropy changes in solution must be included in order to compute the TOF values in line with the experimental results.