Influence of Asymmetrical Ligand Substitution on the Formation, Stability, and Reactivity of Ruthenium(III)-Hypochlorite Complexes.

Abstract

Hypohalites are commonly generated in biological systems, mostly with functions related to defense and immune system response. These hypohalites can bind to metal centers and are known for their strong oxidizing properties that play crucial roles in various biological processes. Herein, we report the synthesis, characterization and reactivity of novel biomimetic Ru(III)-hypochlorite complexes and focus the work on the electronic effects associated with the incorporation of methyl groups in a pentadentate ligand framework in an asymmetric fashion. The intermediates are stable at room temperature and were characterized by mass spectrometry, UV-vis absorption, resonance Raman and EPR spectroscopy. We show for the first time that the resultant ruthenium-hypochlorite adducts function as an electrophilic oxidant and efficiently catalyze hydrogen atom abstraction reactions from phenol and oxygen atom transfer reactions with dimethylsulfide.