Contrasts in the hydrolysis of VOCl3 and VO(NO3)3: a multinuclear magnetic resonance study

Abstract

Controlled hydrolysis of VO(NO₃)₃ in CH₃CN or CH₃NO₂ first gives the dimer V₂O₃(NO₃)_4′ then a complex mixture of polymeric species. In contrast, the hydrolysis of VOCl₃ in CH₃CN gives [VO₂Cl₂]^–, together with some [VOCl₄]^–. The ion [VO₂Cl₂]^– has also been prepared independently, and then converted into [VO₂Cl(NO₃)]^– and [VO₂(NO₃)₂]^–. Species have been characterised by ⁵¹V, ¹⁷O, ¹⁵N, and ¹⁴N n.m.r. spectroscopy, and by stoicheiometry. The ⁵¹V and ¹⁷O chemical shifts are consistent with the anticipated bonding.