Redox Potentials of Cobalt Corrinoids with Axial Ligands Correlate with Heterolytic Co-C Bond Dissociation Energies

Yoshitsugu Morita, Koji Oohora, Akiyoshi Sawada, Takashi Kamachi, Kazunari Yoshizawa, Takashi Hayashi

研究成果: Contribution to journalArticle査読

13 被引用数 (Scopus)

抄録

We investigate the correlations between the redox potentials of nonalkylated cobalt corrinoids and the Co-C bond dissociation energies (BDEs) of the methylated species with an aqua or histidine axial ligand. A set of cobalt corrinoids, cobalamin, and its model systems, which include new version of myoglobin reconstituted with cobalt didehydrocorrin, are investigated. The Co(III)/Co(II) and Co(II)/Co(I) redox potentials of myoglobin reconstituted with cobalt tetradehydrocorrin and didehydrocorrin and the bare cofactors were determined. Density functional theory (DFT) calculations were performed to estimate the Co-C BDEs of the methylated species. It is found that the redox potentials correlate well with the heterolytic BDEs, which are dependent on the electronegativity of the corrinoid frameworks. The present study offers two important insights into our understanding of how enzymes promote the reactions: (i) homolysis is promoted by strong axial ligation and (ii) heterolysis is controlled by the redox potentials, which are regulated by the saturated framework and axial ligation in the enzyme.

本文言語英語
ページ(範囲)1950-1955
ページ数6
ジャーナルInorganic chemistry
56
4
DOI
出版ステータス出版済み - 2 20 2017

All Science Journal Classification (ASJC) codes

  • 物理化学および理論化学
  • 無機化学

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