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Issue 45, 2018
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Mechanistic study of styrene aziridination by iron(IV) nitrides

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Abstract

A combined experimental and computational investigation was undertaken to investigate the mechanism of aziridination of styrene by the tris(carbene)borate iron(IV) nitride complex, PhB(tBuIm)3Fe[triple bond, length as m-dash]N. While mechanistic investigations suggest that aziridination occurs via a reversible, stepwise pathway, it was not possible to confirm the mechanism using only experimental techniques. Density functional theory calculations support a stepwise radical addition mechanism, but suggest that a low-lying triplet (S = 1) state provides the lowest energy path for C–N bond formation (24.6 kcal mol−1) and not the singlet ground (S = 0) state. A second spin flip may take place in order to facilitate ring closure and the formation of the quintet (S = 2) aziridino product. A Hammett analysis shows that electron-withdrawing groups increase the rate of reaction σp (ρ = 1.2 ± 0.2). This finding is supported by the computational results, which show that the rate-determining step drops from 24.6 kcal mol−1 to 18.3 kcal mol−1 when (p-NO2C6H4)CH[double bond, length as m-dash]CH2 is used and slightly increases to 25.5 kcal mol−1 using (p-NMe2C6H4)CH[double bond, length as m-dash]CH2 as the substrate.

Graphical abstract: Mechanistic study of styrene aziridination by iron(iv) nitrides

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Publication details

The article was received on 17 Aug 2018, accepted on 08 Sep 2018 and first published on 10 Sep 2018


Article type: Edge Article
DOI: 10.1039/C8SC03677B
Citation: Chem. Sci., 2018,9, 8542-8552
  • Open access: Creative Commons BY-NC license
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    Mechanistic study of styrene aziridination by iron(IV) nitrides

    Douglas W. Crandell, S. B. Muñoz, J. M. Smith and M. Baik, Chem. Sci., 2018, 9, 8542
    DOI: 10.1039/C8SC03677B

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