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Nonheme iron complex-catalyzed efficient alcohol oxidation by t-BuOOH with N-hydroxyphthalimide (NHPI) as co-catalyst: Implication of high valent iron-oxo species

Title
Nonheme iron complex-catalyzed efficient alcohol oxidation by t-BuOOH with N-hydroxyphthalimide (NHPI) as co-catalyst: Implication of high valent iron-oxo species
Authors
Bae, Jeong MiLee, Myoung MiLee, Seul AhLee, Sun YoungBok, Kwon HeeKim, JinheungKim, Cheal
Ewha Authors
김진흥
SCOPUS Author ID
김진흥scopus
Issue Date
2016
Journal Title
INORGANICA CHIMICA ACTA
ISSN
0020-1693JCR Link1873-3255JCR Link
Citation
vol. 451, pp. 8 - 15
Keywords
Nonheme iron complexesAlcohol oxidationHigh-valent iron-oxo speciestert-Butyl hydroperoxideImidazoleN-hydroxyphthalimide
Publisher
ELSEVIER SCIENCE SA
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Two iron catalysts ([Fe(bpc)Cl-2][ELIN] (la) and [Fe(Me(2)bpb)Cl2][Et3NFI] (lb)) displayed efficient catalysis in oxidation of various alcohols to the corresponding carbonyl products using t-BuOOH as an oxidant in the presence of N-hydroxyphthalimide (NHPI) under mild conditions. la having an electron-withdrawing group showed a little better catalytic activity than that of lb with an electron-donating group. The mechanistic studies through Hammett plot, deuterium isotope effect, and the use of 2-methyl-1-phenylprop2-yl hydroperoxide (MPPH) as a mechanistic probe suggested that the reactive oxidants responsible for the alcohol oxidation possibly involved Fe-lv=0 species, alkoxy radical (Ra), and phthalimide N-oxyl radical (PINO center dot). On the other hand, the presence of imidazole increased the heterolytic cleavage of Fe-OOR intermediate to form Fe-v=0 species and accelerated its O-O bond cleavage rate. In particular, the formation of Fev=0 intermediate via the heterolytic cleavage of Fe-OOR species in the presence of imidazole in the catalytic oxidation systems of nonheme iron complexes with t-BuOOH was substantialized, for the first time, to the best of our knowledge. (C) 2016 Elsevier B.V. All rights reserved.
DOI
10.1016/j.ica.2016.06.03
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자연과학대학 > 화학·나노과학전공 > Journal papers
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