Chiral Co(II) Metal-Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions (Articolo in rivista)

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  • Chiral Co(II) Metal-Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions (Articolo in rivista) (literal)
Anno
  • 2014-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/cs401003d (literal)
Alternative label
  • Tuci, Giulia; Giambastiani, Giuliano; Kwon, Stephanie; Stair, Peter; Snurr, Randall; Rossin, Andrea (2014)
    Chiral Co(II) Metal-Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions
    in ACS catalysis; ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Tuci, Giulia; Giambastiani, Giuliano; Kwon, Stephanie; Stair, Peter; Snurr, Randall; Rossin, Andrea (literal)
Pagina inizio
  • 1032 (literal)
Pagina fine
  • 1039 (literal)
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  • 4 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 8 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino (Firenze), Italy Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM), Via G. Giusti 9, 50121 Firenze, Italy Department of Chemical and Biological Engineering, ?Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States (literal)
Titolo
  • Chiral Co(II) Metal-Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions (literal)
Abstract
  • The chiral Co(II) MOF [Co(L-RR)(H2O)·H2O]n [1; L-RR = (R,R)-thiazolidine-2,4-dicarboxylate] has been exploited in the catalytic oxidation of different alkenes (cyclohexene, (Z)-cyclooctene, 1-octene) using either tert-butyl hydroperoxide (tBuOOH) or molecular oxygen (O2) as oxidants. Different chemoselectivities are observed, both substrate- and oxidantdependent. A moderate enantioselectivity is also obtained in the case of prochiral precursors, revealing the chiral induction ability of the optically pure metal environment. The interaction of O2 with the exposed metal sites in 1 (after material preactivation and consequent removal of the coordinated aquo ligand) has been studied through TPD-MS analysis combined with DFT calculations, with the aim of probing effective oxygen uptake by the heterogeneous catalyst and unraveling the nature of the active species in the catalytic oxidation process under aerobic conditions. Theoretical results indicate the presence of an h1-superoxo species at the cobalt center, with concomitant Co(II) <-> Co(III) oxidation. Finally, the experimental estimation of the O2 adsorption enthalpy is found to be in good agreement with the calculated binding energy. (literal)
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