Journal
CHEMCATCHEM
Volume 7, Issue 17, Pages 2711-2719Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201500584
Keywords
ab initio calculations; homogeneous catalysis; manganese; oxidation; quantum chemistry
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Funding
- UGent GOA grant [01G00710]
- European Research Council through the European Community (ERC) [240483]
- Research Board of Ghent University (BOF)
- Belgian-American educational foundation
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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.
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