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The oxovanadium(IV) complexes LVO and L′VO (L = dianion of 5,14-dihydro-6,8,15.17- tetramethyldibenzo[b.i][1,4.8,11]tetraazacyclotetradecine. H 2 L, and L′ = dianion of 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine, H 2 L′) are redox active as indicated by cyclovoltammetric measurements and confirmed by preparative methods: Reversible oxidation to the corresponding oxovanadium (V) cations is observed at ca. 0.35 V vs. SCE in CH 2 Cl 2 , and these cations are prepared in high yield by oxidation of the oxovanadium(IV) precursors with [(C 5 H 5 ) 2 Fe]SbF 6  (reversible by addition of cobaltocene). Irreversible reduction waves are observed for both complexes in the range -1 .9 to 2.1 V vs. SCE in CH 2 Cl 2 . Preparative reduction of LVO with Na/K alloy affords very unstable anionic oxovanadium(IV) complexes containing a deprotonated or reduced ligand, while with Li[B(C 2 H 5 ) 3 H] in THF the Lewis acid/Lewis base adduct LVOxB(C 2 H 3 ) 3  is isolated. Spectroscopic data including ESR [vanadium(IV)] and  51 V NMR [vanadium(V)] are given and discussed. The complexes LVO and [LVO]SbF 6  have been characterized by single crystal Xray structure determinations.

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Zur Redoxchemie und Struktur von Oxovanadium(IV,V)-KompIexen mit substituierten Dibenzotetraaza[14]annulen Liganden / Redox Chemistry and Structure of Oxovanadium(IV.V) Complexes Containing Substituted Dibenzotetraaza[14]annulene Ligands