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Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound I to Compound II in a Heme Model Study
- Title
- Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound I to Compound II in a Heme Model Study
- Authors
- Fukui, Nami; Li, Xiao-Xi; Nam, Wonwoo; Fukuzumi, Shunichi; Fujii, Hiroshi
- Ewha Authors
- 남원우; Shunichi Fukuzumi
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi
- Issue Date
- 2019
- Journal Title
- INORGANIC CHEMISTRY
- ISSN
- 0020-1669
1520-510X
- Citation
- INORGANIC CHEMISTRY vol. 58, no. 13, pp. 8263 - 8266
- Publisher
- AMER CHEMICAL SOC
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- The electron-transfer (ET) processes from electron-donor substrates to oxoiron(IV) porphyrin pi-cation-radical species (Cpd I) are key steps in their oxygenation reactions. Here, we have evaluated the rate constants of the outer-sphere ET reduction of Cpd I model complexes of meso-tetramesitylporphyrin (1) and 2,7,12,17-tetramesity1-3,8,13,18-tetramethylporphyrin (2) in light of the Marcus theory of ET to determine the ET reorganization energies (lambda). The lambda values of the ligand-centered ET reduction of Cpd I model complexes are much smaller than those of the metal-centered ET reduction of various oxoiron(IV) complexes. Moreover, the lambda value of 1 is larger than that of 2, resulting from the difference in the nature of the a(1u)/a(2u) porphyrin pi-cation radical orbitals.
- DOI
- 10.1021/acs.inorgchem.9b01051
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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