Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 model complex having pentafluorophenylthiolate as an axial ligand

Keishiro Tahara, Ayaka Matsuzaki, Takahiro Masuko, Jun Ichi Kikuchi, Yoshio Hisaeda

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2 Citations (Scopus)

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)7C 1ester](ClO4)2, from H2O to C 6F5S- afforded the B12-thiolate complex. The B12-thiolate model complex was characterized by UV-vis, NMR and ESI-mass spectroscopies. The coordination of C6F 5S- 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.

Original languageEnglish
Pages (from-to)6410-6416
Number of pages7
JournalDalton Transactions
Volume42
Issue number18
DOIs
Publication statusPublished - Jul 15 2013

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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