Mechanistic study of styrene aziridination by iron(iv) nitrides
DC Field | Value | Language |
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dc.contributor.author | Douglas W. Crandell | - |
dc.contributor.author | Salvador B. Munoz, III | - |
dc.contributor.author | Jeremy M. Smith | - |
dc.contributor.author | Mu-Hyun Baik | - |
dc.date.available | 2019-01-04T09:27:27Z | - |
dc.date.created | 2018-12-26 | - |
dc.date.issued | 2018-12 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | https://pr.ibs.re.kr/handle/8788114/5322 | - |
dc.description.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 | - |
dc.description.uri | 1 | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Mechanistic study of styrene aziridination by iron(iv) nitrides | - |
dc.type | Article | - |
dc.type.rims | ART | - |
dc.identifier.wosid | 000451072300004 | - |
dc.identifier.scopusid | 2-s2.0-85057189327 | - |
dc.identifier.rimsid | 66485 | - |
dc.contributor.affiliatedAuthor | Mu-Hyun Baik | - |
dc.identifier.doi | 10.1039/c8sc03677b | - |
dc.identifier.bibliographicCitation | CHEMICAL SCIENCE, v.9, no.45, pp.8542 - 8552 | - |
dc.citation.title | CHEMICAL SCIENCE | - |
dc.citation.volume | 9 | - |
dc.citation.number | 45 | - |
dc.citation.startPage | 8542 | - |
dc.citation.endPage | 8552 | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |