Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a SE2 reaction I2 and RCrL2+, (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H2O)2+ and the fate of RCr(H2O)3+ as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of [(CH3)4N][Co(dmgBF2)2py] and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)