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Synthesis, characterization and crystal structure of a dinuclear iron nitrosyl complex with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl.

ABSTRACT: A new dinuclear iron nitrosyl complex [Fe(2)(C(14)H(12)N(3)S)(2)(NO)(4)] (1) (C(14)H(12)N(3)S = 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl) has been obtained by the reaction of Fe(NO)(2)(CO)(2) with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazole in CH(3)OH under moderate condition. Complex 1 was characterized by IR, UV-vis, electrochemistry and single crystal X-ray diffraction. IR spectrum displays two strong characteristic NO stretching frequencies (nu(NO)) in solution and in solid state. Cyclic voltammetry shows one irreversible, two quasi-reversible and two reversible one-electron reductions and irreversible oxidizations. This result is consistent with the fact that complex 1 is very unstable and ready to lose NO in the air. As showing in the single crystal X-ray diffraction, complex 1 forms a "chair-shape" structure by the connections of two iron centers and S-C-N frames of benzimidazole. The dihedral angle of benzimidazole ring and 2Fe-2S plane is 73.6 degrees . The crystal data are the following: 1, monoclinic, space group P2(1)/c, a = 10.43940(10) A, b = 16.0900(2) A, c = 10.13240(10) A, alpha = 90 degrees , beta = 111.0940(10) degrees , gamma = 90 degrees , V = 1587.89(3) A(3), Z = 4.

SUBMITTER: Wang R

PROVIDER: S-EPMC2905046 | biostudies-literature | 2009 Apr

REPOSITORIES: biostudies-literature

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Synthesis, characterization and crystal structure of a dinuclear iron nitrosyl complex with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl.

Wang Rongming R Xu Wei W Zhang Jian J Li Lijuan L

Journal of molecular structure 20090401 1-3

A new dinuclear iron nitrosyl complex [Fe(2)(C(14)H(12)N(3)S)(2)(NO)(4)] (1) (C(14)H(12)N(3)S = 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl) has been obtained by the reaction of Fe(NO)(2)(CO)(2) with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazole in CH(3)OH under moderate condition. Complex 1 was characterized by IR, UV-vis, electrochemistry and single crystal X-ray diffraction. IR spectrum displays two strong characteristic NO stretching frequencies (nu(NO)) in solution and in solid sta ...[more]

PMID: 20640187

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Project description:We use quantitative experimental and theoretical approaches to characterize the vibrational dynamics of the Fe atom in porphyrins designed to model heme protein active sites. Nuclear resonance vibrational spectroscopy (NRVS) yields frequencies, amplitudes, and directions for 57Fe vibrations in a series of ferrous nitrosyl porphyrins, which provide a benchmark for evaluation of quantum chemical vibrational calculations. Detailed normal mode predictions result from DFT calculations on ferrous nitrosyl tetraphenylporphyrin Fe(TPP)(NO), its cation [Fe(TPP)(NO)]+, and ferrous nitrosyl porphine Fe(P)(NO). Differing functionals lead to significant variability in the predicted Fe-NO bond length and frequency for Fe(TPP)(NO). Otherwise, quantitative comparison of calculated and measured Fe dynamics on an absolute scale reveals good overall agreement, suggesting that DFT calculations provide a reliable guide to the character of observed Fe vibrational modes. These include a series of modes involving Fe motion in the plane of the porphyrin, which are rarely identified using infrared and Raman spectroscopies. The NO binding geometry breaks the four-fold symmetry of the Fe environment, and the resulting frequency splittings of the in-plane modes predicted for Fe(TPP)(NO) agree with observations. In contrast to expectations of a simple three-body model, mode energy remains localized on the FeNO fragment for only two modes, an N-O stretch and a mode with mixed Fe-NO stretch and FeNO bend character. Bending of the FeNO unit also contributes to several of the in-plane modes, but no primary FeNO bending mode is identified for Fe(TPP)(NO). Vibrations associated with hindered rotation of the NO and heme doming are predicted at low frequencies, where Fe motion perpendicular to the heme is identified experimentally at 73 and 128 cm-1. Identification of the latter two modes is a crucial first step toward quantifying the reactive energetics of Fe porphyrins and heme proteins.

Dataset Information

Synthesis, characterization and crystal structure of a dinuclear iron nitrosyl complex with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl.

Publications

Synthesis, characterization and crystal structure of a dinuclear iron nitrosyl complex with 2-mercapto-1-[2-(4-pyridyl)-ethyl]-benzimidazolyl.

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