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Ruthenium carborane complexes: a relationship between the structure, electrochemical properties, and reactivity in catalysis of polymerization processes

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Abstract

The ruthenacarborane complexes of the exo-nido- and closo-structure, namely, diamagnetic exo-nido-5,6,10-[RuCl(PPh3)2]-5,6,10-(μ-H)3-10-H-7,8-(CH3)2-7,8-C2B9H6, 3,3-[Ph2P(CH2) n PPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 4, 5), paramagnetic 3,3-[Ph2P(CH2) n PPh2]-3-Cl-closo-3,1,2-RuC2B9H11 (n = 2–5), and their some ortho-phenylenecycloboronated derivatives, were studied by cyclic voltammetry. All chelate closo-complexes are characterized by reversible redox transitions, while the exo-nido-complex is liable to irreversible oxidation. Shortening of the methylene link in the diphosphine ligand of closo-ruthenacarboranes and/or the introduction of ortho-phenylenecycloboronated moieties and methyl substituents to the carbon atoms of the {C2B9} ligand lead to a decrease in the redox potential and electron density redistribution to the metal atom. A comparison of the experimental results on methyl methacrylate polymerization in the presence of the catalytic systems based on the studied metallacarboranes with the data on their electrochemical characteristics suggests that the efficiency of using the ruthenium complexes as catalysts is mainly determined by steric factors.

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Authors and Affiliations

  1. N. I. Lobachevsky Nizhny Novgorod State University, 23 prosp. Gagarina, 603950, Nizhny Novgorod, Russian Federation

    I. D. Grishin, E. S. Turmina & D. F. Grishin

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    D. I. D’yachihin, S. M. Peregudova & I. T. Chizhevsky

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  1. I. D. Grishin
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  2. E. S. Turmina
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  3. D. I. D’yachihin
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  4. S. M. Peregudova
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  5. I. T. Chizhevsky
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Correspondence to I. D. Grishin.

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Dedicated to the Academician of the Russian Academy of Sciences I. P. Beletskaya on the occasion of her birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0691–0698, March, 2013.

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Grishin, I.D., Turmina, E.S., D’yachihin, D.I. et al. Ruthenium carborane complexes: a relationship between the structure, electrochemical properties, and reactivity in catalysis of polymerization processes. Russ Chem Bull 62, 692–698 (2013). https://doi.org/10.1007/s11172-013-0094-1

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  • DOI: https://doi.org/10.1007/s11172-013-0094-1

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