Mechanistic study of styrene aziridination by iron(iv) nitrides

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Title
Mechanistic study of styrene aziridination by iron(iv) nitrides
Author(s)
Douglas W. Crandell; Salvador B. Munoz, III; Jeremy M. Smith; Mu-Hyun Baik
Publication Date
2018-12
Journal
CHEMICAL SCIENCE, v.9, no.45, pp.8542 - 8552
Publisher
ROYAL SOC CHEMISTRY
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)3FeN. 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 ��p (�� = 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)CHCH2 is used and slightly increases to 25.5 kcal mol-1 using (p-NMe2C6H4)CHCH2 as the substrate. © 2018 The Royal Society of Chemistry
URI
https://pr.ibs.re.kr/handle/8788114/5322
ISSN
2041-6520
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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