Abstract
ABSTRACT
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.