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Axial ligand tuning of a nonheme iron(IV)-oxo unit for hydrogen atom abstraction

Axial ligand tuning of a nonheme iron(IV)-oxo unit for hydrogen atom abstraction
Sastri C.V.Lee J.Oh K.Yoon J.L.Jackson T.A.Ray K.Hirao H.Shin W.Halfen J.A.Kim J.Que Jr. L.Shaik S.Nam W.
Ewha Authors
남원우scopus; 김진흥scopus
Issue Date
Journal Title
Proceedings of the National Academy of Sciences of the United States of America
0027-8424JCR Link
vol. 104, no. 49, pp. 19181 - 19186
The reactivities of mononuclear nonheme iron(IV)-oxo complexes bearing different axial ligands, [Fe IV(O)(TMC)(X)] n+ [where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and X is NCCH 3 (1-NCCH 3), CF 3COO- (1-OOCCF 3), or N 3 - (1-N 3)], and [Fe IV(O)(TMCS)] + (1′-SR) (where TMCS is 1-mercaptoethyl-4,8,11-trimethyl-1,4, 8,11-tetraazacyclotetradecane), have been investigated with respect to oxo-transfer to PPh 3 and hydrogen atom abstraction from phenol O - H and alkylaromatic C - H bonds. These reactivities were significantly affected by the identity of the axial ligands, but the reactivity trends differed markedly. In the oxidation of PPh3, the reactivity order of 1-NCCH 3 > 1-OOCCF 3 > 1-N 3 > 1′-SR was observed, reflecting a decrease in the electrophilicity of iron(IV)-oxo unit upon replacement of CH 3CN with an anionic axial ligand. Surprisingly, the reactivity order was inverted in the oxidation of alkylaromatic C - H and phenol O - H bonds, i.e., 1′-SR > 1-N 3 > 1-OOCCF 3 > 1-NCCH 3. Furthermore, a good correlation was observed between the reactivities of iron(IV)-oxo species in H atom abstraction reactions and their reduction potentials, E p,c, with the most reactive 1′-SR complex exhibiting the lowest potential. In other words, the more electron-donating the axial ligand is, the more reactive the iron(IV)-oxo species becomes in H atom abstraction. Quantum mechanical calculations show that a two-state reactivity model applies to this series of complexes, in which a triplet ground state and a nearby quintet excited-state both contribute to the reactivity of the complexes. The inverted reactivity order in H atom abstraction can be rationalized by a decreased triplet-quintet gap with the more electron-donating axial ligand, which increases the contribution of the much more reactive quintet state and enhances the overall reactivity. © 2007 by The National Academy of Sciences of the USA.
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