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Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortion of the Macrocycle
Author(s) -
Fukuzumi Shunichi,
Nakanishi Ikuo,
Barbe JeanMichel,
Guilard Roger,
Van Caemelbecke Eric,
Guo Ning,
Kadish Karl M.
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990401)38:7<964::aid-anie964>3.0.co;2-o
Subject(s) - manganese , chemistry , electron transfer , semiquinone , planarity testing , photochemistry , kinetics , electron , homogeneous , crystallography , inorganic chemistry , redox , organic chemistry , thermodynamics , physics , quantum mechanics
Slow electron transfer to manganese( iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R 1 =H, Cl, F; R 2 =H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes.