Spectroscopic and structural characterizations of water-soluble peroxo complexes of niobium(V) with N-containing heterocyclic ligands

New water-soluble heteroleptic peroxo complexes of niobiumV have been prepared with N-containing heterocyclic ligands. The compounds correspond to the general formula (gu)x[Nb(O2)3(L)] · nH2O (gu = guanidinium). Three different ligands (L) have been used: picolinic acid (Hpic), picolinic acid N-oxide (HpicO) and pyrazine 2,5-dicarboxylic acid (2,5-H2pzdc). The NbV complexes have been characterized on the basis of elemental and thermal analysis as well as by IR and ESI-mass spectrometry. The crystal structure of the peroxo complex with the picolinato N-oxide ligand, (gu)2[Nb(O2)3(picO)] (II) has been determined, showing an eightfold-coordinated Nb atom surrounded by three peroxide groups and a picO ligand bound in a bidentate mode via the carboxylato and the N-oxide groups. The coordination polyhedron around the metal is a triangular dodecahedron.