Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound i to Compound II in a Heme Model Study

Nami Fukui, Xiao Xi Li, Wonwoo Nam, Shunichi Fukuzumi, Hiroshi Fujii

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

The electron-transfer (ET) processes from electron-donor substrates to oxoiron(IV) porphyrin Ï€-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-tetramesityl-3,8,13,18-tetramethylporphyrin (2) in light of the Marcus theory of ET to determine the ET reorganization energies (λ). The λ 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 λ value of 1 is larger than that of 2, resulting from the difference in the nature of the a1u/a2u porphyrin π-cation-radical orbitals.

Original languageEnglish
Pages (from-to)8263-8266
Number of pages4
JournalInorganic Chemistry
Volume58
Issue number13
DOIs
StatePublished - 1 Jul 2019

Bibliographical note

Funding Information:
This work was supported by grants from JSPS (Grants 25288032 and 17H03032 to H.F. and Grant 16H02268 to S.F.) and CREST (to H.F.) and the NRF of Korea through CRI (Grant NRF-2012R1A3A2048842 to W.N.) and GRL (Grant NRF-2010-00353 to W.N.).

Publisher Copyright:
© 2019 American Chemical Society.

Fingerprint

Dive into the research topics of 'Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound i to Compound II in a Heme Model Study'. Together they form a unique fingerprint.

Cite this