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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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Supplementary files

Article information


Submitted
17 Aug 2018
Accepted
08 Sep 2018
First published
10 Sep 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 8542-8552
Article type
Edge Article

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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