Hydrogen bonding and proton transfer to the trihydride complex [Cp*MoH<inf>3</inf>(dppe)]: IR, NMR, and theoretical investigations

Natalia V. Belkova, Pavel O. Revin, Maria Besora, Miguel Baya, Lina M. Epstein, Agustí Lledós, Rinaldo Poli, Elena S. Shubina, Evgenii V. Vorontsov

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31 Citations (Scopus)


The interaction between [Cp*MoH3(dppe)] (dppe = Ph 2PCH2CH2PPh2) and a variety of proton donors has been investigated by a combination of experiments and DFT calculations. Weak proton donors [2-monofluoroethanol (MFE) and trifluoroethanol (TFE)] allow the determination of basicity factor (Ej = 1.42 ± 0.02) and thermodynamic parameters for the hydrogen bond formation (ΔHHB = -4.9 ± 0.2 and -6.1 ± 0.3 kcal mol -1; ΔSHB = -15.7 ± 0.7 and -20.4 ± 1 cal mol-1 K-1 for MFE and TFE, respectively). For TFE, a stable low-temperature proton-transfer equilibrium (220-240 K) with the cationic classical tetrahydrido derivative [Cp*MoH4(dppe)]+ could be investigated independently by UV/Vis (ΔH°PT = -2.8 ± 0.4 kcal mol-1 and ΔS°PT = -15 ± 2 cal mol-1 K-1) and 1H NMR (ΔH°PT = -2.7 ± 0.5 kcal mol-1 and ΔS°PT = -11 ± 2 cal mol-1 K-1) spectroscopy. Upon warming, however, the tetrahydride evolves by dihydrogen loss and formation of a hydride-free diamagnetic product. Stronger proton donors [hexafluoroisopropanol (HFIP), p-nitrophenol (PNP), perfluoro-tert-butyl alcohol (PFTB), and HBF4·OEt2] lead to more extensive proton transfer at lower donor/Mo ratios. A 1:1 proton-transfer stoichiometry is indicated independently by a titration experiment with UV/Vis monitoring for the [Cp*MoH3(dppe)]-PNP reaction, and by a stopped-flow kinetics investigation for the [Cp*MoH3(dppe)]- HFIP reaction. For all proton-transfer processes investigated, the classical tetrahydrido cation forms directly, without the observation of a nonclassical intermediate. DFT calculations have been carried out on the interaction between TFE and HFIP and the model compound [CpMoH3(dpe)] (dpe = H 2PCH2CH2PH2) both in the gas phase and in CH2Cl2 solvent with the polarizable continuum model and, to a more limited extent, on the full [Cp*MoH3(dppe)] system. A detailed comparison of the observed and calculated frequency shifts for the M-H vibrations is presented. The calculations have explored the relative energy and geometry of various configurations involving either a hydride ligand or the metal as the principal proton-accepting site. They have also probed two principal proton-transfer pathways, leading to the unobserved non-classical intermediate and to the observed classical product. From these studies, it appears that a nonclassical intermediate may be obtained by a kinetically controlled proton transfer to a hydride site, followed by an intramolecular rearrangement through a very low energy barrier. However, a competitive low-energy pathway for direct proton transfer at the metal site is also revealed by the calculations. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Original languageEnglish
Pages (from-to)2192-2209
JournalEuropean Journal of Inorganic Chemistry
Issue number11
Publication statusPublished - 2 Jun 2006


  • DFT calculations
  • Dihydrogen bonding
  • Hydride ligands
  • Molybdenum
  • Proton-transfer mechanism


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