What factors influence the reactivity of C-H hydroxylation and C=C epoxidation by [Fe(IV)(L(ax))(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(O)](n+)

Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry
Wang YiWang Yong

Abstract

Density functional theory is used to investigate geometric structures and mechanisms for hydroxylation and epoxidation from propene for four non-heme iron complexes, [Fe(IV)(L(ax))(TMC)(O)](n+), which are the inverted isomers of [Fe(IV)(O)(TMC)(Lax)](n+) (Lax = acetonitrile (AN), monoanionic trifluoroacetate (TF), azide (N3), thiolate (SR)). The Fe(IV)O unit is found to be sterically less hindered in [Fe(IV)(L(ax))(TMC)(O)](n+) than that in [Fe(IV)(O)(TMC)(L(ax))](n+). Becke, three-parameter, Lee-Yang-Parr (B3LYP) calculations show that hydroxylation and epoxidation proceed via a two-state-reactivity on competing triplet and quintet spin surfaces; and the reactions have been invariably mediated by the S = 2 state. The reaction pathways computed reveal that 2-AN is the most reactive in the four [Fe(IV)(L(ax))(TMC)(O)](n+) complexes; along the reaction pathway, the axial ligand moves away from the iron center, and thus, the energy of the LUMO decreases. The anionic axial ligand, which is more electron releasing than neutral AN, shows a strong overlap of iron orbitals. Thus, the anionic ligand does not move away from the iron center. The H-abstraction is affected by the tunneling contribution, the more electron donation power of t...Continue Reading

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