Coordination of BF4- to oxovanadium(V) complexes, evidenced by the redox potential of oxovanadium(IV/V) couples in CH2Cl2

Kenichi Oyaizu, Eniya Listiani Dewi, Eishun Tsuchida

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Abstract

The oxidation of oxovanadium(IV) complexes [LVIVO] (L = tetradentate Schiff-base ligands such as N,N′-ethylenebis- (salicylideneaminate)(2-) (salen) and N,N′ -2,2-dimethylpropylenebis(salicylideneaminate)(2-) (salpn)) to [LVVO]+, believed to be responsible for the voltammetric response near 0.6 V vs Ag/AgC in CH2Cl2 in the presence of tetrabutylammonium tetrafluoroborate as a supporting electrolyte, is in fact coupled to a homogeneous process where [LVO]+ coordinates BF4- to form a neutral complex formulated as [LVOBF4]. The formation constants for [VO(salen)BF4] and [VO(salpn)BF4] are evaluated to be Ksalen-1 = 1.1 × 102 M-1 and Ksalpn-1 = 1.4 × 10 M-1, respectively. Crystal structure of [VO(salen)BF4] reveals that one of the fluorine atoms in BF4- is so close to the vanadium(V) atom as to be practically bound in the solid state.

Original languageEnglish
Pages (from-to)1070-1075
Number of pages6
JournalInorganic Chemistry
Volume42
Issue number4
DOIs
Publication statusPublished - 2003 Feb 24

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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