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Axial ligand substituted nonheme FeIV=O complexes: observation of near-UV LMCT bands and Fe=O Raman vibrations. 2005
Chivukula V Sastri, and
Mi Joo Park, and
Takehiro Ohta, and
Timothy A Jackson, and
Audria Stubna, and
Mi Sook Seo, and
Jimin Lee, and
Jinheung Kim, and
Teizo Kitagawa, and
Eckard Münck, and
Lawrence Que, and
Wonwoo Nam
Department of Chemistry and Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.
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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