Charge Distribution in Mixed‐Valent Lindqvist‐Type Vanadium Alkoxides
Lagan Arya, Susanne M. Rupf, Yogesh Shandilya, Johann Spandl, Moritz Malischewski, Olaf NachtigallABSTRACT
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.