Chiral Co(II) metal-organic framework in the heterogeneous catalytic oxidation of alkenes under aerobic and anaerobic conditions

Giulia Tuci, Giuliano Giambastiani, Stephanie Kwon, Peter C Stair, Randall Q. Snurr, Andrea Rossin

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The chiral Co(II) MOF [Co(l-RR)(H2O)·H2O] [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 oxidant-dependent. 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 η1-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.

Original languageEnglish
Pages (from-to)1032-1039
Number of pages8
JournalACS Catalysis
Volume4
Issue number3
DOIs
Publication statusPublished - Mar 7 2014

Fingerprint

Catalytic oxidation
Alkenes
Oxidants
Olefins
Metals
Thiazolidines
tert-Butylhydroperoxide
Molecular oxygen
Enantioselectivity
Temperature programmed desorption
Cobalt
Binding energy
Discrete Fourier transforms
Enthalpy
Ligands
Oxygen
Adsorption
Oxidation
Catalysts
Substrates

Keywords

  • alkene oxidation
  • cobalt (II)
  • DFT calculations
  • dioxygen activation
  • heterogeneous catalysis
  • metal-organic frameworks

ASJC Scopus subject areas

  • Catalysis

Cite this

Chiral Co(II) metal-organic framework in the heterogeneous catalytic oxidation of alkenes under aerobic and anaerobic conditions. / Tuci, Giulia; Giambastiani, Giuliano; Kwon, Stephanie; Stair, Peter C; Snurr, Randall Q.; Rossin, Andrea.

In: ACS Catalysis, Vol. 4, No. 3, 07.03.2014, p. 1032-1039.

Research output: Contribution to journalArticle

Tuci, Giulia ; Giambastiani, Giuliano ; Kwon, Stephanie ; Stair, Peter C ; Snurr, Randall Q. ; Rossin, Andrea. / Chiral Co(II) metal-organic framework in the heterogeneous catalytic oxidation of alkenes under aerobic and anaerobic conditions. In: ACS Catalysis. 2014 ; Vol. 4, No. 3. pp. 1032-1039.
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