Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound I to Compound II in a Heme Model Study
- 주제(기타) Chemistry, Inorganic & Nuclear
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2019
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000161213
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/acs.inorgchem.9b01051
- PubMed https://pubmed.ncbi.nlm.nih.gov/31184486
초록/요약
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.
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