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Dihydrogen bonding formed by (hydrido)[hydrotris(pyrazolyl)borato]ruthenium. The effect of ligands on the proton-accepting ability of ruthenium complexes

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Abstract

Reactions of [1,2-bis(diphenylphosphino)ethane](hydrido)[hydrotris(pyrazolyl)borato]-ruthenium with proton donors were studied by IR and 1H NMR spectroscopy in CH2Cl2 over a wide temperature range. Dihydrogen bonding to CF3CH2OH was detected; its spectral and thermodynamic parameters (ΔH° =–3.3±0.2 kcal mol–1, ΔS° =–6.7±0.6 cal mol–1 K–1) were determined. The basicity factor E j of the hydride ligand is 0.81. The H⋯H distance in the dihydrogen-bonded complex (2.05 Å) was estimated from the changes in the spin-lattice relaxation time T 1min of the hydride resonance. Comparison of the results obtained with the literature data revealed a correlation between the length and enthalpy of formation of the dihydrogen bond as well as a correlation between the basicity of the hydride ligand and the tendency of the fragment [ML n ] toward stabilization and oxidative addition of H2.

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Authors and Affiliations

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

    G. A. Silantyev, E. M. Kozinets, O. A. Filippov, E. D. Yakurnova & N. V. Belkova

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  1. G. A. Silantyev
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  2. E. M. Kozinets
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  3. O. A. Filippov
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  4. E. D. Yakurnova
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  5. N. V. Belkova
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Correspondence to N. V. Belkova.

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Dedicated to the 60th anniversary of foundation of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2434—2437, November, 2014.

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Silantyev, G.A., Kozinets, E.M., Filippov, O.A. et al. Dihydrogen bonding formed by (hydrido)[hydrotris(pyrazolyl)borato]ruthenium. The effect of ligands on the proton-accepting ability of ruthenium complexes. Russ Chem Bull 63, 2434–2437 (2014). https://doi.org/10.1007/s11172-014-0759-4

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  • DOI: https://doi.org/10.1007/s11172-014-0759-4

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