Variable coordination mode of chloranilic acid. Synthesis, structure, and electrochemical properties of some osmium complexes

Reaction of chloranilic acid (H2ca) with Os(bpy)2 Br2] (bpy = 2,2'-bipyridine) affords a dinuclear complex of type {Os(bpy)2}2 (ca)]2+, isolated as the perchlorate salt. A similar reaction of H2ca with Os(PPh3)2 (pap)Br2] (pap = 2-(phenylazo)pyridine) affords a dinuclear complex of type {Os(PPh3)2 (pap)}2 (ca)]2+ (isolated as the perchlorate salt) and a mononuclear complex of type Os(PPh3)2 (pap)(ca)]. Reaction of H2ca with Os(PPh3)2(CO)2(HCOO)2] gives a dinuclear complex of type {Os(PPh3)2(CO)2}2 (r-ca)], where r-ca is the two electron reduced form of the chloranilate ligand. The structures of the {Os(PPh3)2 (pap)}2 (ca)](ClO4)2, Os(PPh3)2 (pap)(ca)], and {Os(PPh3)2(CO)2}2 (r-ca)] complexes have been determined by X-ray crystallography. In the {Os(bpy)2}2 (ca)]2+ and {Os(PPh3)2 (pap)}2 (ca)]2+ complexes, the chloranilate dianion is serving as a tetradentate bridging ligand. In the Os(PPh3)2 (pap)(ca)] complex, the chloranilate dianion is serving as a bidentate chelating ligand. In the {Os(PPh3)2(CO)2}2 (r-ca)] complex, the reduced form of the chloranilate ligand (r-ca(4-)) is serving as a tetradentate bridging ligand. All the four complexes are diamagnetic and show intense metal-to-ligand charge-transfer transitions in the visible region. The Os(PPh3)2 (pap)(ca)] complex shows an Os(II)-Os(III) oxidation, followed by an Os(III)-Os(IV) oxidation on the positive side of a standard calomel electrode. The three dinuclear complexes show two successive oxidations on the positive side of SCE. The mixed-valent Os(II)-Os(III) species have been generated in the case of the two chloranilate-bridged complexes by coulometric oxidation of the homovalent Os(II)-Os(II) species. The mixed-valent Os(II)-Os(III) species show intense intervalence charge-transfer transitions in the near-IR region.