Axial ligand substituted nonheme FeIV=O complexes: observation of near-UV LMCT bands and Fe=O Raman vibrations |
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Authors: | Sastri Chivukula V Park Mi Joo Ohta Takehiro Jackson Timothy A Stubna Audria Seo Mi Sook Lee Jimin Kim Jinheung Kitagawa Teizo Münck Eckard Que Lawrence Nam Wonwoo |
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Institution: | Department of Chemistry and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea. |
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Abstract: | Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands. |
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