Paramagnetic Chloro‐, Alkoxo‐, or Azidovanadium(IV) Complexes Supported by an [ONNO]‐Type Amine Bis(phenolate) Ligand

Abstract

AbstractThe reactions between V(N3)2(NMe2)2 or V(OiPr)4 and the chelating dianionic bis(phenoxy)amine ligand [ONNO]H2 afford complexes formulated as [V(N3)2{ONNO}] (1) and [V(OiPr)2{ONNO}] (2). When refluxed in toluene with an excess of Me3SiCl, compound 2 leads to mono‐ or dichloro derivatives [V(Cl)(OiPr){ONNO}] (3) and [VCl2{ONNO}] (4) depending on the experimental conditions. The crystal structures of complexes 1−4 were solved and show in all cases an [ONNO] ligand that has phenolate groups in a trans configuration, with both amino‐nitrogen donor atoms of the ligand coordinated to the octahedral vanadium center. Complexes 1−4 were further characterized by EPR spectroscopy and susceptibility measurement studies typical of d1‐paramagnetic VIV species. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)