title: Synthesis, characterization, Co-S bond reactivity of a vitamin B12 model complex having pentafluorophenylthiolate as an axial ligand.
abstract: Heptamethyl (aquo)(pentafluorophenylthiolate)cobyrinate perchlorate, [(H2O)(C6F5S)Cob(III)7C1ester]ClO4, was synthesized as a B12 model complex having a thiolate ligand in the axial position. The axial ligand change in heptamethyl (diaquo)cobyrinate diperchlorate, [(H2O)2Cob(III)7C1ester](ClO4)2, from H2O to C6F5S(-) afforded the B12-thiolate complex. The B12-thiolate model complex was characterized by UV-vis, NMR and ESI-mass spectroscopies. The coordination of C6F5S(-) to the cobalt center affected the spectroscopic properties of the corrin ring through the electronic interaction between the axial ligand (C6F5S(-)) and the equatorial ligand (corrin). The photolysis of the B12-thiolate model complex led to the homolytic cleavage of the Co(iii)-S bond to form the Co(II) complex and the phenyl thiyl radical. The thermolysis of the B12-thiolate model complex also led to the homolytic cleavage of the Co(III)-S bond. Furthermore, the reactivity of the Co(III)-S bond of the B12-thiolate model complex was applied to the catalytic oxidation of C6F5SH to C6F5S-SC6F5.
authors: Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan.
authors: Keishiro
authors: K
authors: Tahara
authors: Ayaka
authors: A
authors: Matsuzaki
authors: Takahiro
authors: T
authors: Masuko
authors: Jun-ichi
authors: J
authors: Kikuchi
authors: Yoshio
authors: Y
authors: Hisaeda
mesh_terms: D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D003035:Cobalt / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D008024:Ligands; D010084:Oxidation-Reduction; D013455:Sulfur / Q000737:chemistry*; D014805:Vitamin B 12 / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D006845:Hydrocarbons, Fluorinated; D008024:Ligands; D003035:Cobalt; D013455:Sulfur; D014805:Vitamin B 12