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- W2890432142 endingPage "8552" @default.
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- W2890432142 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( t BuIm)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." @default.
- W2890432142 created "2018-09-27" @default.
- W2890432142 creator A5018106788 @default.
- W2890432142 creator A5030203661 @default.
- W2890432142 creator A5046251854 @default.
- W2890432142 creator A5072221187 @default.
- W2890432142 date "2018-01-01" @default.
- W2890432142 modified "2023-09-26" @default.
- W2890432142 title "Mechanistic study of styrene aziridination by iron(<scp>iv</scp>) nitrides" @default.
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- W2890432142 doi "https://doi.org/10.1039/c8sc03677b" @default.
- W2890432142 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/6251402" @default.
- W2890432142 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30568778" @default.
- W2890432142 hasPublicationYear "2018" @default.
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