Interaction between a Transition-Metal Fluoride and a Transition-Metal Hydride: Water-Mediated Hydrofluoric Acid Evolution Following Fluoride Solvation

Abstract

The reaction between the nickel(II) PCP pincer fluoride complex ((tBu)PCP)Ni(F) [(tBu)PCP = 2,6-C6H3(CH2P(t)Bu2)2] and the tungsten(II) carbonyl hydride CpW(H)(CO)3 (Cp = η(5)-C5H5(-)) leads to hydrofluoric acid evolution and formation of the bimetallic isocarbonylic species [CpW(CO)2(μ-κ,C:κ,O-CO)···Ni((tBu)PCP)]. The process has been monitored through multinuclear ((19)F, (31)P{(1)H}, (1)H) variable-temperature NMR spectroscopy, collecting (19)F T1 data values for a fluoride ligand bound to a transition metal. The extremely short relaxation time (minimum value of 13 ms at 193 K) is ascribed to the large chemical shift anisotropy of the Ni-F bond (688 ppm). The in-depth NMR analysis has revealed that the fluoride-hydride interaction is not direct but water-mediated, at odds with what was previously observed for the "hydride-hydride" case ((tBu)PCP)Ni(H)/CpW(H)(CO)3. Kinetic measurements have unveiled that the first step of the overall mechanism is thought to be solvation of the fluoride ligand (as a result of Ni-F···H2O hydrogen bonding), while further reaction of the solvated fluoride with CpW(H)(CO)3 is extremely slow and competes with the side reaction of fluoride replacement by a water molecule on the nickel center to form the [((tBu)PCP)Ni(H2O)](+) aquo species. Finally, density functional theory analysis of the solvation process through a discrete + continuum model has been accomplished, at the M06//6-31+G(d,p) level of theory, to support the mechanistic hypothesis.