title: Nature of Cp*MoO2+ in water and intramolecular proton-transfer mechanism by stopped-flow kinetics and density functional theory calculations.
abstract: A stopped-flow study of the Cp*MoO3- protonation at low pH (down to zero) in a mixed H2O-MeOH (80:20) solvent at 25 degrees C allows the simultaneous determination of the first acid dissociation constant of the oxo-dihydroxo complex, [Cp*MoO(OH)2]+ (pKa1 = -0.56), and the rate constant of its isomerization to the more stable dioxo-aqua complex, [Cp*MoO2(H2O)]+ (k-2 = 28 s-1). Variable-temperature (5-25 degrees C) and variable-pressure (10-130 MPa) kinetics studies have yielded the activation parameters for the combined protonation/isomerization process (k-2/Ka1) from Cp*MoO2(OH) to [Cp*MoO2(H2O)]+, viz., DeltaH++= 5.1 +/- 0.1 kcal mol-1, DeltaS++ = -37 +/- 1 cal mol-1 K-1, and DeltaV++ = -9.1 +/- 0.2 cm3 mol-1. Computational analysis of the two isomers, as well as the [Cp*MoO2]+ complex resulting from the dissociation of water, reveals a crucial solvent effect on both the isomerization and the water dissociation energetics. Introducing a solvent model by the conductor-like polarizable continuum model and especially by explicitly inclusion of up to three water molecules in the calculations led to the stabilization of the dioxo-aqua species relative to the oxo-dihydroxo isomer and to the substantial decrease of the energy cost for the water dissociation process. The presence of a water dissociation equilibrium is invoked to account for the unusually low effective acidity (pKa1' = 4.19) of the [Cp*MoO2(H2O)]+ ion. In addition, the computational study reveals the positive role of external water molecules as simultaneous proton donors and acceptors, having the effect of dramatically lowering the isomerization energy barrier.
authors.affiliation: Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany.
authors.forename: Joo-Eun
authors.initials: JE
authors.lastname: Jee
authors.forename: Aleix
authors.initials: A
authors.lastname: Comas-Vives
authors.forename: Chiara
authors.initials: C
authors.lastname: Dinoi
authors.forename: Gregori
authors.initials: G
authors.lastname: Ujaque
authors.forename: Rudi
authors.initials: R
authors.lastname: van Eldik
authors.forename: Agustí
authors.initials: A
authors.lastname: Lledós
authors.forename: Rinaldo
authors.initials: R
authors.lastname: Poli