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

The reaction of [(Me/BnTPEN)Ru-II(NCCH3)](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 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.

Automated summary

The reaction of [(Me/BnTPEN)Ru-II(NCCH3)](2+) with mCPBA in the presence of chloride ions generated a novel (Me/BnTPEN)Ru-III-OCl species. This hypochlorite adduct can also be obtained by the direct reaction of (L)Ru-II complexes with NaOCl and HClO4. The ruthenium hypochlorite adduct catalyzes hydrogen atom abstraction reactions of phenols and their derivatives.