Modeling the Oxygen Vacancy at a Molecular Vanadium(III) Silica-Supported Catalyst

Here we report on the use of a silanol-decorated polyoxotungstate, [SbW₉O₃₃(^tBuSiOH)₃]^3- (1), as a molecular support to describe the coordination of a vanadium atom at a single-site on silica surfaces. By reacting [V(Mes)₃thf] (Mes = 2,4,6-trimethylphenyl) with 1 in tetrahydrofuran, the vanadium(III) derivative [SbW₉O₃₃(^tBuSiO)₃V(thf)]^3- (2) was obtained. Compound 2 displays the paramagnetic behavior expected for a d²-V^III high spin complex (SQUID measurements) with a triplet electronic ground state (ca. 30 kcalmol^-1 more stable than the singlet, from DFT calculations). Compound 2 proves to be a reliable model for reduced isolated-vanadium atom dispersed on silica surfaces [(-Si - O)₃V^III(OH₂)], an intermediate that is often proposed in a Mars-van Krevelen type mechanism for partial oxidation of light alcohols. Oxidation of 2 under air produced the oxo-derivative [SbW₉O₃₃(^tBuSiO)₃VO]^3- (3). In compound 2, the d²-electrons are localized in degenerated d(V) orbitals, whereas in the electronically analogous bireduced-[SbW₉O₃₃(tBuSiO)₃VO]^5-, 3(2e), one electron is localized on d(V) orbital and the second one is delocalized on the polyoxotungstic framework, leading to a unique case of a bireduced heteropolyanion derivative with completely decoupled d¹-V(IV) and d¹-W(V). Our body of experimental results (EPR, magnetic measurements, spectroelectrochemical studies, Raman spectroscopy) and theoretical studies highlights (i) the role of the apical ligand coordination, i.e., thf (σ-donor) vs oxo (π-donor), in destabilizing or stabilizing the d(V) orbitals relative to the d(W) orbitals, and (ii) a geometrical distortion of the O₃VO entity that causes a splitting of the degenerated orbitals and the stabilization of one d(V) orbital in the bireduced compound 3(2e).