화학공학소재연구정보센터
Applied Catalysis A: General, Vol.545, 44-53, 2017
Highly efficient C-Cl bond cleavage and unprecedented C-C bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc](2-) species results in rapid cleavage of the C-(sp)(3)-Cl, C-(sp)(2)-Cl and aromatic C-(sp)(2)-Cl bonds. Bis(p-chlorophenyl)methanone (BPC12) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C-Cl bond cleavage products, due to an unprecedented C-C bond cleavage reaction that is followed by the formation of a C-O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C-Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.