Synthesis, Spectroscopic and Theoretical Studies of Ruthenafuran and Osmafuran Prepared by Activation of Ynone in Alcohol

Abstract

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.