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Dalton Trans. 2011 Jun 7;40(21):5697-705. doi: 10.1039/c1dt10027k. Epub 2011 Apr 11.

The radical mechanism of cobalt(II) porphyrin-catalyzed olefin aziridination and the importance of cooperative H-bonding.

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  • 1Homogeneous and Supramolecular Catalysis group, Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam.

Abstract

The mechanism of cobalt(II) porphyrin-mediated aziridination of styrene with PhSO(2)N(3) was studied by means of DFT calculations. The computations clearly indicate the involvement of a cobalt 'nitrene radical' intermediate in the Co(II)(por)-catalyzed alkene aziridination. The addition of styrene to this species proceeds in a stepwise fashion via radical addition of the 'nitrene radical'C to the C=C double bond of styrene to form a γ-alkyl radical intermediate D. The thus formed tri-radical species D easily collapses in an almost barrierless ring closure reaction (TS3) to form the aziridine, thereby regenerating the cobalt(II) porphyrin catalyst. The radical addition of the 'nitrene radical'C to the olefin (TS2) proceeds with a comparable barrier as its formation (TS1), thus providing a good explanation for the first order kinetics in both substrates and the catalyst observed experimentally. Formation of C is clearly accelerated by stabilization of C and TS1 via hydrogen bonding between the S=O and N-H units. The computed radical-type mechanism agrees well with all available mechanistic and kinetic information. The computed free energy profile readily explains the superior performance of the Co(II)(porAmide) system with H-bond donor functionalities over the non-functionalized Co(TPP).

PMID:
21483935
[PubMed]
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