DC Field | Value | Language |
---|---|---|
dc.contributor.author | Crandell, Douglas W. | ko |
dc.contributor.author | Munoz, Salvador B., III | ko |
dc.contributor.author | Smith, Jeremy M. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.date.accessioned | 2018-12-20T08:01:45Z | - |
dc.date.available | 2018-12-20T08:01:45Z | - |
dc.date.created | 2018-12-14 | - |
dc.date.created | 2018-12-14 | - |
dc.date.issued | 2018-12 | - |
dc.identifier.citation | CHEMICAL SCIENCE, v.9, no.45, pp.8542 - 8552 | - |
dc.identifier.issn | 2041-6520 | - |
dc.identifier.uri | http://hdl.handle.net/10203/248685 | - |
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 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)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.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Mechanistic study of styrene aziridination by iron(iv) nitrides | - |
dc.type | Article | - |
dc.identifier.wosid | 000451072300004 | - |
dc.identifier.scopusid | 2-s2.0-85057189327 | - |
dc.type.rims | ART | - |
dc.citation.volume | 9 | - |
dc.citation.issue | 45 | - |
dc.citation.beginningpage | 8542 | - |
dc.citation.endingpage | 8552 | - |
dc.citation.publicationname | CHEMICAL SCIENCE | - |
dc.identifier.doi | 10.1039/c8sc03677b | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Crandell, Douglas W. | - |
dc.contributor.nonIdAuthor | Munoz, Salvador B., III | - |
dc.contributor.nonIdAuthor | Smith, Jeremy M. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | SOLVATION FREE-ENERGIES | - |
dc.subject.keywordPlus | OXYGEN-ATOM TRANSFER | - |
dc.subject.keywordPlus | MOLECULAR CALCULATIONS | - |
dc.subject.keywordPlus | CATALYZED AZIRIDINATION | - |
dc.subject.keywordPlus | STEREOSPECIFIC SYNTHESIS | - |
dc.subject.keywordPlus | ALKENE AZIRIDINATION | - |
dc.subject.keywordPlus | 2-STATE REACTIVITY | - |
dc.subject.keywordPlus | N-H | - |
dc.subject.keywordPlus | C-H | - |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.