title: 4-amino- and 4-nitrodipicolinatovanadium(V) complexes and their hydroxylamido derivatives: synthesis, aqueous, and solid-state properties.
abstract: A number of 4-substituted, dipicolinatodioxovanadium(V) complexes and their hydroxylamido derivatives were synthesized to characterize the solid state and solution properties of five- and seven-coordinate vanadium(V) complexes. The X-ray crystal structures of Na[VO2dipic-NH2].2H2O (2) and K[VO2dipic-NO2] (3) show the vanadium adopting a distorted, trigonal-bipyramidal coordination environment similar to the parent coordination complex, [VO2dipic]- (1), reported previously as the Cs+ salt. The observed differences in the chemical shifts of the complexes both in the 1H (ca. 0.7-1.4 ppm) and 51V (ca. 1-11 ppm) NMR spectra were consistent with the electron-donating or electron-withdrawing properties of the substituent groups, respectively. Stoichiometric addition of a series of hydroxylamine ligands (H2NOH, MeHNOH, Me2NOH, and Et2NOH) to complexes 1-3 led to the formation of seven-coordinate vanadium(V) complexes. The X-ray crystal structure of [VO(dipic)(Me2NO)(H2O)].0.5H2O (1c) was found to be similar to the previously characterized complexes [VO(dipic)(H2NO)(H2O)] (1a) and [VO(dipic)(OO-tBu)(H2O)]. While only slight differences in the 1H NMR spectra were observed upon addition of the hydroxylamido ligand, the signals in the 51V NMR spectra change by up to 100 ppm. The addition of the hydroxylamido ligand increased the complex stability of complexes 2 and 3. Evidence for a nonstoichiometric redox reaction was found for the monoalkyl hydroxylamine ligand. The reaction of an unsaturated five-coordinate species with a hydroxylamine to form a seven-coordinate vanadium complex will, in general, dramatically increase the amounts of the vanadium compound that remain intact at pH values near neutral.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: Jason J
authors.initials: JJ
authors.lastname: Smee
authors.forename: Jason A
authors.initials: JA
authors.lastname: Epps
authors.forename: Guillaume
authors.initials: G
authors.lastname: Teissedre
authors.forename: Mandy
authors.initials: M
authors.lastname: Maes
authors.forename: Nichola
authors.initials: N
authors.lastname: Harding
authors.forename: Luqin
authors.initials: L
authors.lastname: Yang
authors.forename: Bharat
authors.initials: B
authors.lastname: Baruah
authors.forename: Susie M
authors.initials: SM
authors.lastname: Miller
authors.forename: Oren P
authors.initials: OP
authors.lastname: Anderson
authors.forename: Gail R
authors.initials: GR
authors.lastname: Willsky
authors.forename: Debbie C
authors.initials: DC
authors.lastname: Crans
mesh_terms: D000577:Amides / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010848:Picolinic Acids / Q000737:chemistry; D012995:Solubility; D017968:Vanadium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D000577:Amides; D010848:Picolinic Acids; D017968:Vanadium Compounds; D014867:Water; C004860:dipicolinic acid