Russian Chemical Bulletin

, Volume 64, Issue 12, pp 2806–2810 | Cite as

Hydrogen bonds, coordination isomerism, and catalytic dehydrogenation of alcohols with the bifunctional iridium pincer complex \(^{{{\left( {HOC{H_2}} \right)}_2}}\left( {P{C_{s{p^3}}}P} \right)\)IrHCl

  • G. A. Silantyev
  • E. M. Titova
  • O. A. Filippov
  • E. I. Gutsul
  • D. Gelman
  • N. V. BelkovaEmail author
Full Articles


The reaction of iridium(iii) hydride complex 1 based on the pincer dibenzobarrelene ligand \(^{{{\left( {HOC{H_2}} \right)}_2}}\left( {P{C_{s{p^3}}}P} \right)\) with pyridine proceeds stepwise to show different reactivities of the starting fac-isomers 1A and 1B. The kinetic product of the reaction is mer-complex 2 with a trans disposition of the pyridine and hydride ligands. Isomerization into the thermodynamic product 2′ containing pyridine in the cis-position with regard to hydride proceeds slowly. The estimation of activation parameters (ΔH and ΔS ) shows that the change in the geometry of fac-complexes upon coordination of pyridine occurs through an associative transition state, while isomerization of the mer-complexes is a dissociative process. The isomers of complex 1 and its pyridine-containing derivatives 2 and 2′ are shown to exhibit different reactivities in the formation of dihydrogen bond and the catalytic dehydrogenation of PriOH under model conditions.

Key words

transition metal hydrides hydrogen bonds NMR spectroscopy IR spectroscopy 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    N. V. Belkova, L. M. Epstein, E. S. Shubina, Eur. J. Inorg. Chem., 2010, 3555–3565.Google Scholar
  2. 2.
    N. V. Belkova, E. S. Shubina, L. M. Epstein, Acc. Chem. Res., 2005, 38, 624–631.CrossRefGoogle Scholar
  3. 3.
    W. K. Fung, X. Huang, M. L. Man, S. M. Ng, M. Y. Hung, Z. Lin, C. P. Lau, J. Am. Chem. Soc., 2003, 125, 11539–11544.CrossRefGoogle Scholar
  4. 4.
    V. Y. Kukushkin, A. J. L. Pombeiro, Inorg. Chim. Acta, 2005, 358, 1–21.CrossRefGoogle Scholar
  5. 5.
    A. Urakawa, F. Jutz, G. Laurenczy, A. Baiker, Chem. Eur. J., 2007, 13, 3886–3899.CrossRefGoogle Scholar
  6. 6.
    G. Zeng, S. Sakaki, K.-I. Fujita, H. Sano, R. Yamaguchi, ACS Catal., 2014, 4, 1010–1020.CrossRefGoogle Scholar
  7. 7.
    D. Gelman, R. Romm, in Organometallic Pincer Chemistry, Ed. G. van Koten, D. Milstein, Springer, Berlin—Heidelberg, 2013, Vol. 40, Ch. 10, pp. 289–317.Google Scholar
  8. 8.
    S. Musa, I. Shaposhnikov, S. Cohen, D. Gelman, Angew. Chem. Intern. Ed., 2011, 50, 3533–3537.CrossRefGoogle Scholar
  9. 9.
    G. A. Silantyev, O. A. Filippov, S. Musa, D. Gelman, N. V. Belkova, K. Weisz, L. M. Epstein, E. S. Shubina, Organometallics, 2014, 33, 5964–5973.CrossRefGoogle Scholar
  10. 10.
    T. W. Whaley, D. G. Ott, J. Label. Comp., 1974, 10, 283–286.CrossRefGoogle Scholar
  11. 11.
    Z. G. Specht, D. B. Grotjahn, C. E. Moore, A. L. Rheingold, Organometallics, 2013, 32, 6400–6409.CrossRefGoogle Scholar
  12. 12.
    D. B. Grotjahn, J. E. Kraus, H. Amouri, M.-N. Rager, A. L. Cooksy, A. J. Arita, S. A. Cortes-Llamas, A. A. Mallari, A. G. DiPasquale, C. E. Moore, L. M. Liable-Sands, J. D. Golen, L. N. Zakharov, A. L. Rheingold, J. Am. Chem. Soc., 2010, 132, 7919–7934.CrossRefGoogle Scholar
  13. 13.
    K. D. Atkinson, M. J. Cowley, P. I. P. Elliott, S. B. Duckett, G. G. R. Green, J. Lуpez-Serrano, A. C. Whitwood, J. Am. Chem. Soc., 2009, 131, 13362–13368.CrossRefGoogle Scholar
  14. 14.
    K. D. Atkinson, M. J. Cowley, S. B. Duckett, P. I. P. Elliott, G. G. R. Green, J. Lуpez-Serrano, I. G. Khazal, A. C. Whitwood, Inorg. Chem., 2009, 48, 663–670.CrossRefGoogle Scholar
  15. 15.
    S. Li, M. B. Hall, Organometallics, 1999, 18, 5682–5687.CrossRefGoogle Scholar
  16. 16.
    B. Rybtchinski, Y. Ben-David, D. Milstein, Organometallics, 1997, 16, 3786–3793.CrossRefGoogle Scholar
  17. 17.
    O. A. Filippov, N. V. Belkova, L. M. Epstein, A. Lledos, E. S. Shubina, Comp. Theor. Chem., 2012, 998, 129–140.CrossRefGoogle Scholar
  18. 18.
    P. G. Jessop, R. H. Morris, Coord. Chem. Rev., 1992, 121, 155–284.CrossRefGoogle Scholar
  19. 19.
    G. J. Kubas, Chem. Rev., 2007, 107, 4152–4205.CrossRefGoogle Scholar
  20. 20.
    S. Musa, O. A. Filippov, N. V. Belkova, E. S. Shubina, G. A. Silantyev, L. Ackermann, D. Gelman, Chem. Eur. J., 2013, 19, 16906–16909.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • G. A. Silantyev
    • 1
  • E. M. Titova
    • 1
  • O. A. Filippov
    • 1
  • E. I. Gutsul
    • 1
  • D. Gelman
    • 2
  • N. V. Belkova
    • 1
    Email author
  1. 1.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation
  2. 2.Institute of ChemistryThe Hebrew University of Jerusalem, Edmond Safra CampusJerusalemIsrael

Personalised recommendations