Generation of Ru(III)-hypochlorite with resemblance to the heme-dependent haloperoxidase enzyme.

The reaction of [(Me/BnTPEN)Ru II (NCCH 3 )] 2+ (BnTPEN = N 1 -benzyl- N 1 , N 2 , N 2 -tris(pyridine-2-ylmethyl)ethane-1,2-diamine and MeTPEN = N 1 -methyl- N 1 , N 2 , N 2 -tris(pyridine-2-ylmethyl)ethane-1,2-diamine) with m CPBA in the presence of chloride ions in CH 3 CN : H 2 O generated a novel (Me/BnTPEN)Ru III -OCl species at room temperature. This hypochlorite adduct could also be obtained by the direct reaction of NaOCl and HClO 4 with (L)Ru II complexes. The current study mimics the synthesis of a metal hypochlorite adduct in a similar fashion as in the heme-dependent haloperoxidase enzyme. As an electrophilic oxidant, the ruthenium hypochlorite adduct catalyzes hydrogen atom abstraction reactions of phenols and their derivatives.