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Redox transformations of polynuclear molybdenum alkoxides and their interaction with nitrogenase substrates: experimental and theoretical study

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Abstract

The experimental and theoretical study of the electronic structure and IR spectra of the CO-containing molybdenum(0) alkoxide complexes of different nuclearity was carried out. The binding energy of the dinitrogen ligand was calculated for the tetranuclear K4[Mo(OR)(CO)3]4 complexes catalyzing dinitrogen reduction. The theoretical study of structural changes for the 20-electron reduction of the catalytic cluster of the octanuclear [Mg2Mo8O22(MeO)6(MeOH)4]2− complex was performed. The interaction of the reduced cluster with the nitrogenase substrate was considered. Probable coordination modes of N2, C2H2, and CO were analyzed, as well as the protonation reactions of the acetylene complexes, giving rise to two- and four-electron reduction products. The results of quantum chemical calculations are in good agreement with the experimental regularities observed for the catalytic reduction of the substrates in the presence of the Mo-Mg cluster.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    T. A. Savinykh, T. A. Bazhenova, N. V. Kovaleva & A. F. Shestakov

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  1. T. A. Savinykh
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  2. T. A. Bazhenova
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  3. N. V. Kovaleva
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  4. A. F. Shestakov
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Correspondence to T. A. Savinykh.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 185–196, January, 2012.

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Savinykh, T.A., Bazhenova, T.A., Kovaleva, N.V. et al. Redox transformations of polynuclear molybdenum alkoxides and their interaction with nitrogenase substrates: experimental and theoretical study. Russ Chem Bull 61, 188–199 (2012). https://doi.org/10.1007/s11172-012-0026-5

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  • DOI: https://doi.org/10.1007/s11172-012-0026-5

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