Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(iv) complexes
نویسندگان
چکیده
Max-Planck Institut für Chemische Energi Mülheim an der Ruhr, Germany. E-mail: [email protected] Department of Chemistry, Center for Metals 207 Pleasant St. SE, Minneapolis, Minnesota † Electronic supplementary information ( VTVH MCD intensity analysis of comp Boltzmann populations of S 1⁄4 1 magneti magnetic eld, derivation of the excited transition, determination of the C-term transitions for complex 1, VTVH MCD computed MCD spectrum of complex 2. S Cite this: Chem. Sci., 2015, 6, 2909
منابع مشابه
Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(iv) complexes† †Electronic supplementary information (ESI) available: VT MCD spectra, VT and VTVH MCD intensity analysis of complex 1, energies, S x, S z values and Boltzmann populations of S = 1 magnetic sublevels as a function of the applied magnetic field, derivation of the excited states arising from the 1b2 → 2b1 transition, determination of the C-term sign of band 1 and the E(2e → 2a1) transitions for complex 1, VTVH MCD spectra, VTVH simulations and the computed MCD spectrum of complex 2. See DOI: 10.1039/c4sc03268c Click here for additional data file.
High-valent iron(IV)-oxo species are key intermediates in the catalytic cycles of a range of O2-activating iron enzymes. This work presents a detailed study of the electronic structures of mononuclear ([FeIV(O)(L)(NCMe)]2+, 1, L = tris(3,5-dimethyl-4-methoxylpyridyl-2-methyl)amine) and dinuclear ([(L)FeIV(O)(μ-O)FeIV(OH)(L)]3+, 2) iron(IV) complexes using absorption (ABS), magnetic circular dic...
متن کاملInversion of axial chirality in coordinated bis-β-diketonato ligands.
Mononuclear and dinuclear ruthenium(III) complexes with bis-β-diketonato ligands (denoted by [Ru(acac)(2)(L-LH)] and [Ru(acac)(2)(L-L)Ru(acac)(2)], respectively) were synthesized, where acac, L-LH(-) and L-L(2-) denote acetylacetonato, monoprotonated and unprotonated bis-β-diketonato ligands, respectively. The following three ligands were used as the bis-β-diketonato ligand (L-L(2-)): 1,2-diace...
متن کاملIron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase
Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]-/2-), to ferric and ferrous tetrathiolates ([Fe(SR)4]-/2-), to diferric and mixed-va...
متن کاملDNA binding and bending by dinuclear complexes comprising ruthenium polypyridyl centres linked by a bis(pyridylimine) ligand.
The interaction of enantiomerically pure dinuclear complexes of the form [Ru2(L-L)4L1]4+ (where L-L = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) and L1 = bis(pyridylimine) ligand ((C5H4N)CN(C6H4))2CH2)) with ct-DNA have been investigated by absorbance, circular dichroism, fluorescence displacement assays, thermal analysis, linear dichroism and gel electrophoresis. The complexes all bin...
متن کاملComputational Insights into Five- versus Six-Coordinate Iron Center in Ferrous Soybean Lipoxygenase
Soybean lipoxygenase (SLO) serves as a prototype for fundamental understanding of hydrogen tunneling in enzymes. Its reactivity depends on the active site structure around a mononuclear, nonheme iron center. The available crystal structures indicate five-coordinate iron, while magnetic circular dichroism experiments suggest significant populations of both five-coordinate (5C) and six-coordinate...
متن کامل