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Mononuclear Antimony(V) Catecholate Complexes with Additional Pyridine Ligands

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Abstract

A series of triarylantimony(V) complexes with p-dimethylaminopyridine and р-cyanopyridine of the general formulas [(Cat)SbAr3(р-Me2N–Py)] (complexes I–IV) and [(Cat)SbAr3(р-CN–Py)] (complexes V–VII) has been synthesized. Their molecular structures and electrochemical properties have been studied. 3,6-Di-tert-butyl-o-benzoquinone, 4,5-piperazine-1,4-diyl-3,6-di-tert-butyl-o-benzoquinone, and 4,5-dichloro-3,6-di-tert-butyl-o-benzoquinone are used as redox-active ligands. The molecular structures of several complexes in the crystalline state are determined by X-ray diffraction analysis (CIF files CCDC nos. 1974173 (I ⋅ 0.5toluene), 1974174 (II ⋅ 2toluene), 1974175 (V), 1974176 (VI ⋅ hexane), and 1974177 (VII)). All complexes have a distorted octahedral structure, and an additional neutral pyridine ligand occupies one of the apical positions. Electrochemical transformations of the complexes are studied by cyclic voltammetry in a dichloromethane solution. The introduction of substituted pyridine into the molecule of the complex does not change the electrooxidation mechanism of the complexes. For all complexes with р-dimethylaminopyridine, both oxidation potentials are shifted to the cathodic region (0.13–0.21 V for the potential of the first oxidation process and to 0.3–0.4 V for the potential of the second oxidation process). A similar shift for the complex with p-cyanopyridine is less pronounced (0.05 V for the potential of the first oxidation process of complex V as compared to that of complex I).

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ACKNOWLEDGMENTS

The study was carried out using the equipment of “Analytical Center of the IOMC RAS” (Zentr Kolektivnogo Polzovaniya) in G.A. Razuvaev Institute of Organometallic Chemistry RAS with the financial support of the Federal objective program “Research and development in priority directions of advancement of science and technology complex of Russia for 2014-2020” (Unique project identifier is RFMEFI62120X0040).

Funding

This work was performed in the accordance with the state assignment of the Razuvaev Institute of Organometallic Chemistry (Russian Academy of Sciences).

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Authors and Affiliations

  1. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 603600, Nizhny Novgorod, Russia

    L. S. Okhlopkova, E. V. Baranov & A. I. Poddel’skii

  2. Southern Research Center, Russian Academy of Sciences, 344006, Rostov-on-Don, Russia

    I. V. Smolyaninov

Authors
  1. L. S. Okhlopkova
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  2. I. V. Smolyaninov
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  3. E. V. Baranov
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  4. A. I. Poddel’skii
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Correspondence to A. I. Poddel’skii.

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Dedicated to I.L. Eremenko on the occasion of his 70th birthday

Translated by E. Yablonskaya

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Okhlopkova, L.S., Smolyaninov, I.V., Baranov, E.V. et al. Mononuclear Antimony(V) Catecholate Complexes with Additional Pyridine Ligands. Russ J Coord Chem 46, 466–476 (2020). https://doi.org/10.1134/S1070328420060081

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  • DOI: https://doi.org/10.1134/S1070328420060081

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