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

Research output: Contribution to journalArticle

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

Fingerprint

Vitamin B 12
Ligands
Thermolysis
Catalytic oxidation
Photolysis
Cobalt
Nuclear magnetic resonance
Spectroscopy
perchlorate
corrin

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 model complex having pentafluorophenylthiolate as an axial ligand. / Tahara, Keishiro; Matsuzaki, Ayaka; Masuko, Takahiro; Kikuchi, Jun Ichi; Hisaeda, Yoshio.

In: Dalton Transactions, Vol. 42, No. 18, 15.07.2013, p. 6410-6416.

Research output: Contribution to journalArticle

Tahara, Keishiro ; Matsuzaki, Ayaka ; Masuko, Takahiro ; Kikuchi, Jun Ichi ; Hisaeda, Yoshio. / Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 model complex having pentafluorophenylthiolate as an axial ligand. In: Dalton Transactions. 2013 ; Vol. 42, No. 18. pp. 6410-6416.
@article{6368d7ccfa4e416c8aedba5f6703e37c,
title = "Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 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)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.",
author = "Keishiro Tahara and Ayaka Matsuzaki and Takahiro Masuko and Kikuchi, {Jun Ichi} and Yoshio Hisaeda",
year = "2013",
month = "7",
day = "15",
doi = "10.1039/c3dt00042g",
language = "English",
volume = "42",
pages = "6410--6416",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "18",

}

TY - JOUR

T1 - Synthesis, characterization, Co-S bond reactivity of a vitamin B 12 model complex having pentafluorophenylthiolate as an axial ligand

AU - Tahara, Keishiro

AU - Matsuzaki, Ayaka

AU - Masuko, Takahiro

AU - Kikuchi, Jun Ichi

AU - Hisaeda, Yoshio

PY - 2013/7/15

Y1 - 2013/7/15

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84879921824&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84879921824&partnerID=8YFLogxK

U2 - 10.1039/c3dt00042g

DO - 10.1039/c3dt00042g

M3 - Article

C2 - 23463441

AN - SCOPUS:84879921824

VL - 42

SP - 6410

EP - 6416

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 18

ER -