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Mechanistic investigation on oxygen transfer with the manganese-salen complex

(2015) CHEMCATCHEM. 7(17). p.2711-2719
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UGent GOA 01G00710
Abstract
The best-known application of salen complexes is the use of a chiral ligand loaded with manganese to form the Jacobsen complex. This organometallic catalyst is used in the epoxidation of unfunctionalized olefins and can achieve very high selectivities. Although this application was proposed many years ago, the mechanism of oxygen transfer remains a question until now. In this paper, the epoxidation mechanism is investigated by an ab initio kinetic modeling study. First of all a proper DFT functional is selected that yields the correct ordering of the various spin states. Our results show that the epoxidation proceeds via a radical intermediate. If we start from the radical intermediate, these results can explain the experiments with radical probes. The subtle influences in the transition state using the full Jacobsen catalyst explain the product distribution observed experimentally.
Keywords
UNFUNCTIONALIZED OLEFINS, ENANTIOSELECTIVE EPOXIDATION, (SALEN)MN-CATALYZED EPOXIDATION, (SALEN)MN(III) COMPLEXES, ASYMMETRIC EPOXIDATION, MEDIATED EPOXIDATION, SPIN STATES, ALKENES, OXIDATION, CATALYSTS, ab initio calculations, homogeneous catalysis, manganese, oxidation, quantum chemistry

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Citation

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Chicago
Bogaerts, Thomas, Sebastian Wouters, Pascal Van Der Voort, and Veronique Van Speybroeck. 2015. “Mechanistic Investigation on Oxygen Transfer with the Manganese-salen Complex.” Chemcatchem 7 (17): 2711–2719.
APA
Bogaerts, Thomas, Wouters, S., Van Der Voort, P., & Van Speybroeck, V. (2015). Mechanistic investigation on oxygen transfer with the manganese-salen complex. CHEMCATCHEM, 7(17), 2711–2719.
Vancouver
1.
Bogaerts T, Wouters S, Van Der Voort P, Van Speybroeck V. Mechanistic investigation on oxygen transfer with the manganese-salen complex. CHEMCATCHEM. 2015;7(17):2711–9.
MLA
Bogaerts, Thomas, Sebastian Wouters, Pascal Van Der Voort, et al. “Mechanistic Investigation on Oxygen Transfer with the Manganese-salen Complex.” CHEMCATCHEM 7.17 (2015): 2711–2719. Print.
@article{6940493,
  abstract     = {The best-known application of salen complexes is the use of a chiral ligand loaded with manganese to form the Jacobsen complex. This organometallic catalyst is used in the epoxidation of unfunctionalized olefins and can achieve very high selectivities. Although this application was proposed many years ago, the mechanism of oxygen transfer remains a question until now. In this paper, the epoxidation mechanism is investigated by an ab initio kinetic modeling study. First of all a proper DFT functional is selected that yields the correct ordering of the various spin states. Our results show that the epoxidation proceeds via a radical intermediate. If we start from the radical intermediate, these results can explain the experiments with radical probes. The subtle influences in the transition state using the full Jacobsen catalyst explain the product distribution observed experimentally.},
  author       = {Bogaerts, Thomas and Wouters, Sebastian and Van Der Voort, Pascal and Van Speybroeck, Veronique},
  issn         = {1867-3880},
  journal      = {CHEMCATCHEM},
  language     = {eng},
  number       = {17},
  pages        = {2711--2719},
  title        = {Mechanistic investigation on oxygen transfer with the manganese-salen complex},
  url          = {http://dx.doi.org/10.1002/cctc.201500584},
  volume       = {7},
  year         = {2015},
}

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