Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

We report the synthesis of vanadium(V) oxo complex 1 with a pincer-type dianionic mesoionic carbene (MIC) ligand L-1 and the general formula [VOCl(L-1)]. A comparison of the structural (SC-XRD), electronic (UV-vis), and electrochemical (cyclic voltammetry) properties of 1 with the benzimidazolinylidene congener 2 (general formula [VOCl(L-2)]) shows that the MIC is a stronger donor also for early transition metals with low d-electron population. Since electrochemical studies revealed both complexes to be reversibly reduced, the stronger donor character of MICs was not only demonstrated for the vanadium(V) but also for the vanadium(IV) oxidation state by isolating the reduced vanadium(IV) complexes [Co( Cp*)(2)][1] and [Co(Cp*)(2)][2] ([Co(Cp*)(2)] = decamethylcobaltocenium). The electronic structures of the compounds were investigated by computational methods. Complex 1 was found to be a moderate precursor for salt metathesis reactions, showing selective reactivity toward phenolates or secondary amides, but not toward primary amides and phosphides, thiophenols, or aryls/alkyls donors. Deoxygenation with electron-rich phosphines failed to give the desired vanadium(III) complex. However, treatment of the deprotonated ligand precursor with vanadium(III) trichloride resulted in the clean formation of the corresponding MIC vanadium(III) complex 6, which undergoes a clean two-electron oxidation with organic azides yielding the corresponding imido complexes. The reaction with TMS-N-3 did not afford a nitrido complex, but instead the imido complex 10. This study reveals that, contrary to popular belief, MICs are capable of supporting early transition-metal complexes in a variety of oxidation states, thus making them promising candidates for the activation of small molecules and redox catalysis.

Automated summary

This study reports the synthesis of a vanadium(V) oxo complex with a pincer-type MIC ligand, and demonstrates that MICs are stronger donors for early transition metals with low d-electron population. The electronic and electrochemical properties were compared with a benzimidazolinylidene congener, showing reversible reduction in both vanadium(V) and vanadium(IV) oxidation states. Computational methods were used to investigate the electronic structures of the compounds. The study highlights the potential of MICs in supporting early transition-metal complexes in various oxidation states for small molecule activation and redox catalysis.