title: Probing heme vibrational anisotropy: an imidazole orientation effect?
abstract: The complete iron vibrational spectrum of the five-coordinate high-spin complex [Fe(OEP)(2-MeHIm)], where OEP = octaethylporphyrinato and 2-MeHIm = 2-methylimidazole, has been obtained by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS) data. Measurements have been made in three orthogonal directions, which provides quantitative information for all iron motion. These experimental data, buttressed by density functional theory (DFT) calculations, have been used to define the effects of the axial ligand orientation. Although the axial imidazole removes the degeneracy in the in-plane vibrations, the imidazole orientation does not appear to control the direction of the in-plane iron motion. This is in contrast to the effect of the imidazolate ligand, as defined by DFT calculations, which does have substantial effects on the direction of the in-plane iron motion. The axial NO ligand has been found to have the strongest orientational effect (Angew. Chem., Int. Ed., 2010, 49, 4400). Thus the strength of the directional properties are in the order NO > imidazolate > imidazole, consistent with the varying strength of the Fe-ligand bond.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Qian
authors.initials: Q
authors.lastname: Peng
authors.forename: Ming
authors.initials: M
authors.lastname: Li
authors.forename: Chuanjiang
authors.initials: C
authors.lastname: Hu
authors.forename: Jeffrey W
authors.initials: JW
authors.lastname: Pavlik
authors.forename: Allen G
authors.initials: AG
authors.lastname: Oliver
authors.forename: E Ercan
authors.initials: EE
authors.lastname: Alp
authors.forename: Michael Y
authors.initials: MY
authors.lastname: Hu
authors.forename: Jiyong
authors.initials: J
authors.lastname: Zhao
authors.forename: J Timothy
authors.initials: JT
authors.lastname: Sage
authors.forename: W Robert
authors.initials: WR
authors.lastname: Scheidt
mesh_terms: D016880:Anisotropy; D056831:Coordination Complexes / Q000737:chemistry*; D006418:Heme / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D007501:Iron / Q000737:chemistry; D011789:Quantum Theory; D014732:Vibration
chemical_list: D056831:Coordination Complexes; D007093:Imidazoles; D006418:Heme; C029899:imidazole; D007501:Iron
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