Electronic structures and absorption spectra properties of complex 8-（（trimethoxysilyl）methylthio）quinoline.SnCh in gas phase and MeCN media have been investigated by using DFT/TD-DFT method. The calculated lowest-energy absorption band shows different mechanisms under these two conditions, and it bears LMCT/LLCT/ILCT character in MeCN solution and LLCT/ILCT character in gas phase. The calculated absorption bands of the title complex in MeCN solvent are in good agreement with the experimental results, and calculation results indicate that the very weak experimentally observed lowest-energy absorption band of the title complex in MeCN solvent originates from the spin-forbidden singlet-triplet transitions.
The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31+G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C—N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31+G(d, p) level of theory based on the po-larizable continuum model (CPCM). In water the first mechanism (path A) is also favored.
ZHANG Chang1 & XUE Ying2? 1 College of Chemistry and Environment Protection Engineering, Southwest University for Nationalities, Chengdu 610041, China
