Charge Distribution in Mixed‐Valent Lindqvist‐Type Vanadium Alkoxides

The binding mode and relative position of tripodal ligands influence the charge distribution in Lindqvist‐type vanadium alkoxides. The stronger the delocalization of d ‐electrons is decreased, the further shifted are the observed redox events to higher potentials. X‐ray crystallographic data of different {V IV/V 6 (tripod) 2 } structures is evaluated, and valence sum calculations are used to assign oxidation states to chemically inequivalent vanadium positions in such hexanuclear aggregates. The impact of varying the charge distribution in {V IV/V 6 } species is discussed by comparing reduction potentials derived from voltammetric experiments. In this way, a new group of {V IV/V 6 (tripod) 2 } isomers is characterized and related to known cis ‐ and trans ‐{V IV/V 6 (tripod) 2 } isomers.