The structure, stability, and reactivity of oxalato-monoperoxovanadium(V) in solution

Abstract

In order to understand the solution chemistry of an oxalato-monoperoxovanadium(V) complex (K 3 [VO(O 2 )(C 2 O 4 ) 2 ] Á ½H 2 O, mpVox), the solid and solution-state NMR characteristics, transformation behavior, and exchange phenomena in the solution are described in this article. NMR experimental and theoretical results indicated that the vanadium of mpVox in solid and solution state are seven coordinate. However, some geometric parameters tend to change upon dissolution. The dynamic transformation of mpVox in solution was investigated using NMR, IR, and UV-Vis. The reduction product is oxalato-bisoxovanadate. Concentration, pH, and temperature affect this transformation. 51 V NMR investigation on the system of mpVox with picolinc acid showed that two oxalates are substituted to produce [VO(O 2 )(ox)(pic)] 2À and [VO(O 2 )(pic) 2 ] À .