Synthesis, spectroscopic and theoretical studies of ruthenafuran and osmafuran prepared by activation of ynone in alcohol

Ruthenafuran and osmafuran monocationic complexes [Ru([14]aneS4)(C∧O)]⁺ or [M(bpy)₂(C∧O)]⁺ (C∧O = anionic bidentate chelate [C(OR)CHC(Ph)-O]^-; [14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane; M = Ru, Os; bpy = 2,2′-bipyridine) have been prepared from reactions between phenyl-ynone HC-C(CO)Ph and [Ru([14]aneS4)Cl₂] or [M(bpy)₂Cl₂] in alcoholic solvents ROH. The formation of metal-vinylidene intermediate, followed by nucleophilic attack by RO^-, and carbonyl group coordination to the metal center are believed to be the key steps in the formation of these metallafurans. The nature of the anionic C∧O ligand was investigated by electrochemical, spectroscopic, and theoretical means.