Electronic versatility of vanadium in tris-chelates with redox-active ligands

Spectroscopic and computational examination of the neutral tris-dioxolene complex [V(dbcat)(3)] (dbcat(2-) = 3,6-di-tert-butylcatecholate) reveals a Class III mixed-valent ground state. The radical is stabilised by delocalisation across the ligands mediated by the energy matched d orbital manifold of the V(v) centre. This electronic structure is compared to the tris-dithiolene and tris-diimine analogues that possess V(iv) and V(ii) ions, respectively.

Automated summary

Spectroscopic and computational examination reveals a Class III mixed-valent ground state for the neutral tris-dioxolene complex [V(dbcat)(3)]. The radical is stabilized by delocalization across the ligands mediated by the V(v) center's energy matched d orbital manifold. This electronic structure differs from the tris-dithiolene and tris-diimine analogues with V(iv) and V(ii) ions, respectively.