title: Aerobic oxidation of pinacol by vanadium(V) dipicolinate complexes: evidence for reduction to vanadium(III).
abstract: The reactivity of vanadium complexes bearing the ligand dipicolinic acid (H(2)dipic) with alcohols has been explored. Dipic vanadium complexes are able to catalyze the aerobic oxidative C-C bond cleavage of pinacol. Reaction under anaerobic conditions allowed for isolation of a V(III) mu-oxo dimer, supporting the involvement of V(III) in aerobic oxidation reactions. Stoichiometric oxidation of unactivated aliphatic alcohols has also been observed, with oxidation of cyclobutanol producing cyclobutanone in 93% yield. The absence of ring-opening products in this reaction provides further support for the involvement of V(III) intermediates.
authors.affiliation: Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: Susan K
authors.initials: SK
authors.lastname: Hanson
authors.forename: R Tom
authors.initials: RT
authors.lastname: Baker
authors.forename: John C
authors.initials: JC
authors.lastname: Gordon
authors.forename: Brian L
authors.initials: BL
authors.lastname: Scott
authors.forename: Andrew D
authors.initials: AD
authors.lastname: Sutton
authors.forename: David L
authors.initials: DL
authors.lastname: Thorn
mesh_terms: D000332:Aerobiosis; D002072:Butylene Glycols / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D010848:Picolinic Acids / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D017968:Vanadium Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D002072:Butylene Glycols; D008024:Ligands; D010848:Picolinic Acids; D017968:Vanadium Compounds; C004860:dipicolinic acid