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Synthesis of mono- and dinuclear vanadium complexes and their reactivity toward dehydroperoxidation of alkyl hydroperoxides

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, and 51V NMR spectroscopy, as well as mass spectrometry and X-ray diffraction. Furthermore, they were tested toward their catalytic...

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Hauptverfasser: Schmidt, Anna-Corina (VerfasserIn) , Hermsen, Marko (VerfasserIn) , Rominger, Frank (VerfasserIn) , Trapp, Oliver (VerfasserIn) , Schaub, Thomas (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: January 24, 2017
In: Inorganic chemistry
Year: 2017, Jahrgang: 56, Heft: 3, Pages: 1319-1332
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b02322
Online-Zugang:Verlag, Volltext: http://dx.doi.org/10.1021/acs.inorgchem.6b02322
Verlag, Volltext: https://doi.org/10.1021/acs.inorgchem.6b02322
Volltext
Verfasserangaben:Anna-Corina Schmidt, Marko Hermsen, Frank Rominger, Richard Dehn, Joaquim Henrique Teles, Ansgar Schäfer, Oliver Trapp, and Thomas Schaub
Beschreibung
Zusammenfassung: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, and 51V 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.
Beschreibung:Gesehen am 18.05.2018
Beschreibung:Online Resource
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b02322

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