DFT studies of the degradation mechanism of methyl mercury activated by a sulfur-rich ligand.

摘要: We describe theoretical insights into the mechanism of Hg–C bond protonolysis in methyl mercury coordinated by tris(2-mercapto-1-tert-butylimidazolyl)hydroborato ligand, structural and functional analogue organomercurial lyase MerB. Different cleavage pathways including both frontside backside attack transition states were systematically studied hybrid density method B3LYP. Dependence activation on primary sulfur coordination number was elaborated, conceptual DFT indexes suggested to be more appropriate than gross charge atom sites interpreting dependence. Furthermore, absence configurational inversion MerB-catalyzed reactions accounted for examinations present system. Lastly, a rationalization provided about choice between different characteristics four-center six-center ones.