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.