Synthesis, characterization and pulse radiolysis of cobalt(II) complexes of 2-picolinate and polypyridyl ligands.

Complexes of the type [Co(pic)(2)(LL)], where pic = picolinate; LL = (H(2)O)(2) (1), 2,2'-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3) and dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4) have been synthesized and characterized by elemental analysis, IR, UV-visible and (1)H-NMR spectroscopy. Complex 2 crystallized from a mixture of chloroform and methanol in orthorhombic crystal system, space group Iba2. Complex 3 crystallizes from chloroform in monoclinic crystal system, space group P12(1)/a1 and in a mixture of water and methanol in triclinic crystal system, space group P1. Co(II)/Co(III) oxidation potentials have been determined by cyclic voltammetry and the concomitant spectral changes measured by spectroelectrochemistry. The reactions of one electron reducing (e(-)(aq), (CH(3))(2)*COH and CO(2)(*-)) and one electron oxidizing ( OH) radicals with the above metal complexes have been studied by pulse radiolysis. The rate constants for the reaction of e(-)(aq) and *OH radicals with the complexes are of the order of 10(10) and 10(9) dm(3) mol(-1) s(-1), respectively. The reaction of hydrated electron (e(-)(aq)) with the complexes results in the formation of a ligand radical anion species which decays by either protonation of ligand or reduction of metal by intramolecular electron transfer resulting in cobalt(I) species. The reaction of *OH radical forms the OH-adducts of the ligand.