0000000000299417
AUTHOR
Lina M. Epstein
Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]
The present contribution reports experimental and computational investigations of the interaction between [Cp*Fe(dppe)H] and different proton donors (HA). The focus is on the structure of the proton transfer intermediates and on the potential energy surface of the proton transfer leading to the dihydrogen complex [Cp*Fe(dppe)(H2)]+. With p-nitrophenol (PNP) a UV/Visible study provides evidence of the formation of the ion-pair stabilized by a hydrogen bond between the nonclassical cation [Cp*Fe(dppe)(H2)]+ and the homoconjugated anion ([AHA]-). With trifluoroacetic acid (TFA), the hydrogen-bonded ion pair containing the simple conjugate base (A-) in equilibrium with the free ions is observed…
Hydrogen bonding and proton transfer involving the trihydride complexes Cp*M(dppe)H 3 (M = Mo, W) and fluorinated alcohols: the competitive role of the hydride ligands and metal
International audience; 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 foun…