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Updated: May 13, 2026

Preparation of SNS Cobalt(II) Pincer Model Complexes of Liver Alcohol Dehydrogenase
Published on: March 19, 2020
Synthesis, characterization, Co-S bond reactivity of a vitamin B12 model complex having pentafluorophenylthiolate as
Keishiro Tahara1, Ayaka Matsuzaki, Takahiro Masuko
1Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan.
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.
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