Carbon–Sulfur Bond Formation between a Ruthenium‐Coordinated Thiyl Radical and Methyl Ketones

A metal-coordinated thiyl radical was revealed by the electrochemical oxidation of a ruthenium(III)–thiolate in acetone (and related ketones). The subsequent reaction between the radical intermediate and acetone resulted in CS bond formation and ultimately a ruthenium(III)–thioether product (see picture). A mechanism that involves reaction of the enol tautomer of acetone with the radical is proposed.