Hydrogen bonding and proton transfer involving the trihydride complexes Cp*M(dppe)H3 (M = Mo,W) and fluorinated alcohols: the competitive role of the hydride ligands and metal |
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| Authors: | Andrieu J. Belkova N. V. Besora M. Collange E. Epstein L. M. Lledós A. Poli R. Revin P. O. Shubina E. S. Vorontsov E. V. |
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| Affiliation: | (1) Laboratory of Synthesis and Electrosynthesis of Organometallic Compounds, Gabriel Science Faculty, University of Burgundy, 6 Gabriel boulv., 2100 Dijon, France;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation;(3) Department of Chemistry, University of Barcelona, 08193 Bellaterra, Spain |
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| Abstract: | The protonation of complexes Cp*M(dppe)H3 (dppe is ethylenebis(diphenylphosphine), M = Mo (1), W (2)) by a variety of fluorinated alcohols of different acid strength (FCH2CH2OH, CF3CH2OH, (CF3)2CHOH, and (CF3)3COH) was investigated experimentally by the variable temperature spectroscopic methods (IR, NMR) and stopped-flow technique (UV-Vis). The structures of the hydrogen-bonded and proton transfer products were studied by DFT calculations. In agreement with the calculation results, the IR data suggest that the initial hydrogen bond is established with a hydride site for complex 1 and with the metal site for complex 2. However, no intermediate dihydrogen complex found theoretically was detected experimentally on the way to the final classical tetrahydride product. |
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| Keywords: | transition metal polyhydrides IR spectroscopy UV-Vis NMR spectroscopy hydrogen bonding proton transfer |
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