Derivate des Hydrazins als Liganden in Vanadium(III)-, -(IV)- und -(V)-Komplexen. Darstellung und Charakterisierung von [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O / Substituted Hydrazines as Ligands in Vanadium(III), -(IV) and -(V) Complexes. Synthesis and Characterization of [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)]·2H2O , [VO(dipic) (NHNHCO2Me)], [VO(dipic)(NH2NHCO2Me)], [VO(dipic)(NHNHCSPh)] und [VO('ONO')(NHNHCOPh)]·2H2O

Abstract

The reaction of [VO(dipic)(H2O)2]·2H2O with benzoylhydrazine, thiobenzoylhydrazine and O-methylcarbazate yields [V(dipic)(NH2NHCOPh)(H2O)2][VO(dipic)(NHNCOPh)·2H2O (1), [V0(dipic)(NHNHCO2Me)] (2), [VO(dipic)(NH2NHCO2Me)] (3) and [VO(dipic)(NHNHCSPh)] (4). 1 is probably formed in solution by redox disproportionation. The reactions giving 2,3 and 4 also involve redox processes with atmospheric oxygen as oxidant and the respective hydrazine as reductant. [VO('ONO')(NHNHCOPh)]·H2O (5) was formed using aqua-oxo-salicylaldehyde-L-alaninato-vanadium(IV) as precursor. The structures of 1,2,3 and 5 have been determined by single crystal X-ray crystallography. The cation of 1 has a seven-coordinated vanadium(III) center with the two H2O molecules at the apices of a pentagonal bipyramide, the anion contains the doubly deprotonated hydrazido( 2-) ligand NHNCOPh2- as N,O-chelate. 2 and 3 have very similar structures, but differ in the oxidation state of the vanadium atom and in the degree of deprotonation of the hydrazine. In 3 neutral NH2NHCOOMe and in 2 the single deprotonated hydrazido(l -) ligand NHNHCOOMe- are bound as N,O-chelates, with the O-donor in rrans-position to the VO group. The remaining coordination sites are occupied by the ONO-donating dinegative dipic ligand. 5, where dipic is replaced by the three-dentate salicylaldehyde-benzoyl-hydrazone, has a very similar structure to 2. 4 with a VO3N2S coordination sphere is the first vanadiun (V) complex containing the N,S-donating hydrazido(l-) ligand NHNHCSPh-. The following parameters are characteristic for the bonding of the NHNHR- and NHNR2- ligands in 1,2 and 5: V-N 189 ± 1 pm, N-N 134 ± 1 pm and V-N-N 122 ± 2°.