title: Synthesis of Mono- and Dinuclear Vanadium Complexes and Their Reactivity toward Dehydroperoxidation of Alkyl Hydroperoxides.
abstract: Several vanadium(V) complexes with either dipic-based or Schiff base ligands were synthesized. The complexes were fully characterized by elemental analysis, IR,1H,13C, and51V NMR spectroscopy, as well as mass spectrometry and X-ray diffraction. Furthermore, they were tested toward their catalytic deperoxidation behavior and a significant difference between 4-heptyl hydroperoxide and cyclohexyl hydroperoxide was observed. In the case of 4-heptyl hydroperoxide, the selectivity toward the corresponding ketone was higher than with cyclohexyl hydroperoxide. DFT calculations performed on the vanadium complex showed that selective decomposition of secondary hydroperoxides with vanadium(V) to yield the corresponding ketone and water is indeed energetically feasible. The computed catalytic path, involving cleavage of the O-O bond, hydrogen transfer, release of ketone/water, and finally addition of hydroperoxide, can proceed without the generation of radical species.
authors.affiliation: Catalysis Research Laboratory (CaRLa) , Im Neuenheimer Feld 584, 69120 Heidelberg, Germany.
authors.forename: Anna-Corina
authors.initials: AC
authors.lastname: Schmidt
authors.affiliation: Catalysis Research Laboratory (CaRLa) , Im Neuenheimer Feld 584, 69120 Heidelberg, Germany.|BASF SE , Quantum Chemistry & Molecular Simulation Catalysis, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany.
authors.forename: Marko
authors.initials: M
authors.lastname: Hermsen
authors.affiliation: Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg , Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Rominger
authors.affiliation: BASF SE , Synthesis & Homogeneous Catalysis, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany.
authors.forename: Richard
authors.initials: R
authors.lastname: Dehn
authors.affiliation: BASF SE , Synthesis & Homogeneous Catalysis, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany.
authors.forename: Joaquim Henrique
authors.initials: JH
authors.lastname: Teles
authors.affiliation: BASF SE , Quantum Chemistry & Molecular Simulation Catalysis, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany.
authors.forename: Ansgar
authors.initials: A
authors.lastname: Schäfer
authors.affiliation: Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg , Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
authors.forename: Oliver
authors.identifier: http://orcid.org/0000-0002-3594-5181
authors.initials: O
authors.lastname: Trapp
authors.affiliation: Catalysis Research Laboratory (CaRLa) , Im Neuenheimer Feld 584, 69120 Heidelberg, Germany.|BASF SE , Synthesis & Homogeneous Catalysis, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany.
authors.forename: Thomas
authors.identifier: http://orcid.org/0000-0003-2332-0376
authors.initials: T
authors.lastname: Schaub