Binary, Ternary, and Quarternary Complexes of Ruthenium(II) Involving the Flexidentate ONNS Donor Mono(4-(4-tolyl)thiosemicarbazone) of 2,6-Diacetylpyridine (L(2)H). First Report on Ruthenium Complexes of a Mono(thiosemicarbazone) of a Diketone: Crystal Structure of [Ru(L(2))(PPh(3))(2)]ClO(4).

A series of Ru(II) complexes of the ONNS donor ligand mono(4-(4-tolyl)thiosemicarbazone) of 2,6-diacetylpyridine (L(2)H) synthesized by using three different ruthenium-containing starting materials RuCl(3).xH(2)O, Ru(PPh(3))(3)Cl(2), and [Ru(NH(3))(5)Cl]Cl(2) are reported. Chemical and electrochemical studies of the complexes [Ru(L(2))(PPh(3))(2)]ClO(4) (1), [Ru(L(2))(PPh(3))(2)]Cl (2), [Ru(L(2))(PPh(3))]ClO(4).EtOH (3), [Ru(L(2))(PPh(3))(bpy)]ClO(4) (4), [Ru(L(2))(PPh(3))(ophen)]ClO(4) (5), [Ru(L(2))(2)] (6), and [Ru(L(2))(L(2)H)]Cl (7) have been carried out. The structure of the compound [Ru(L(2))(PPh(3))(2)]ClO(4) (1) has been determined by single-crystal X-ray diffraction techniques. The crystals are triclinic, space group P&onemacr; with a = 12.716(1) Å, b = 13.213(1) Å, c = 15.951(1) Å, alpha = 87.66(1) degrees, beta = 73.81(1) degrees, gamma = 70.93(1) degrees, and Z = 2, where the deprotonated ligand mono(4-(4-tolyl)thiosemicarbazone) of 2,6-diacetylpyridine (L(2)) is chelated to the Ru(II) center through the oxygen of the carbonyl group, pyridine ring nitrogen, imine nitrogen, and the thiolate sulfur atoms. Strong coordination of the carbonyl group suggested from its IR spectral characteristics has been confirmed from the appreciable shortening of the Ru-O bond and lengthening of the C=O bond in the structure of 1.