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

Abstract

The reaction of [(Me/BnTPEN)Ru^II(NCCH₃)]²⁺ (BnTPEN = N¹-benzyl-N¹,N²,N²-tris(pyridine-2-ylmethyl)ethane-1,2-diamine and MeTPEN = N¹-methyl-N¹,N²,N²-tris(pyridine-2-ylmethyl)ethane-1,2-diamine) with mCPBA in the presence of chloride ions in CH₃CN : H₂O 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 HClO₄ 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.