DC Field | Value | Language |
---|---|---|
dc.contributor.author | Baek, Seung-Yeol | ko |
dc.contributor.author | Kang, Dahye | ko |
dc.contributor.author | Kamitani, Masahiro | ko |
dc.contributor.author | Kwon, Seongyeon | ko |
dc.contributor.author | Kurogi, Takashi | ko |
dc.contributor.author | Solowey, Douglas P. | ko |
dc.contributor.author | Chen, Chun-Hsing | ko |
dc.contributor.author | Pink, Maren | ko |
dc.contributor.author | Carroll, Patrick J. | ko |
dc.contributor.author | Mindiola, Daniel J. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.date.accessioned | 2017-10-23T01:56:28Z | - |
dc.date.available | 2017-10-23T01:56:28Z | - |
dc.date.created | 2017-10-10 | - |
dc.date.created | 2017-10-10 | - |
dc.date.created | 2017-10-10 | - |
dc.date.created | 2017-10-10 | - |
dc.date.issued | 2017-09 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.139, no.36, pp.12804 - 12814 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/226422 | - |
dc.description.abstract | The complex (PNP)Ti=(CHBu)-Bu-t((CH2Bu)-Bu-t) (PNP = N[2-P(i)p(r2)-4-methylphenyl](2-)) dehydrogenates cyclohexane to cyclohexene by forming a transient low-valent titanium-alkyl species, [(PNP)Ti((CH2Bu)-Bu-t)], which reacts with 2 equiv of quinoline (Q) at room temperature to form (H3CBu)-Bu-t and a Ti(IV) species where the less hindered C-2=N-1 bond of Qis ruptured and coupled to another equivalent of Q, The product isolated from this reaction is an imide with a tethered cycloamide group, (PNP)Ti=N[C18H13N] (1). Under photolytic conditions, intramolecular C-H bond activation across the imide moiety in 1 occurs to form 2, and thermolysis reverses this process. The reaction of 2 equiv of isoquinoline (Iq) with intermediate [(PNP)Ti((CH2Bu)-Bu-t)] results in regioselective cleavage of the C-I=N-2 and C-1-H bonds, which eventually couple to form complex 3, a constitutional isomer of 1. Akin to 1, the transient [(PNP)Ti((CH2Bu)-Bu-t)] complex can ring-open and couple two pyridine molecules, to produce a close analogue of 1, complex (PNP)Ti=N[C10H9N] (4). Multinudear and multidimensional NMR spectra confirm structures for complexes 1-4, whereas solid-state structural analysis reveals the structures of 2, 3, and 4. DFT calculations suggest an unprecedented Mechanism for ring-opening of Q wheat the reactive intermediate in the low-spin manifold crosses over to the high-spin surface to access a low-energy transition state but returns to the low-spin surface immediately. This double spin-crossover constitutes a rare example of a two-state reactivity, which is key for enabling the reaction at room temperature. The regioselective behavior of Iq ring-opening is found to be due to electronic effects, where the aromatic resonance of the bicycle is maintained during the key C-C coupling event. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Room-Temperature Ring-Opening of Quinoline, lsoquinoline, and Pyridine with Low-Valent Titanium | - |
dc.type | Article | - |
dc.identifier.wosid | 000411043900069 | - |
dc.identifier.scopusid | 2-s2.0-85029603763 | - |
dc.type.rims | ART | - |
dc.citation.volume | 139 | - |
dc.citation.issue | 36 | - |
dc.citation.beginningpage | 12804 | - |
dc.citation.endingpage | 12814 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/jacs.7b07433 | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Kamitani, Masahiro | - |
dc.contributor.nonIdAuthor | Kurogi, Takashi | - |
dc.contributor.nonIdAuthor | Solowey, Douglas P. | - |
dc.contributor.nonIdAuthor | Chen, Chun-Hsing | - |
dc.contributor.nonIdAuthor | Pink, Maren | - |
dc.contributor.nonIdAuthor | Carroll, Patrick J. | - |
dc.contributor.nonIdAuthor | Mindiola, Daniel J. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | CARBON MULTIPLE BONDS | - |
dc.subject.keywordPlus | HYDRODENITROGENATION CATALYSIS | - |
dc.subject.keywordPlus | HYDRAZIDO COMPOUNDS | - |
dc.subject.keywordPlus | SILICA-ALUMINA | - |
dc.subject.keywordPlus | N-HETEROCYCLES | - |
dc.subject.keywordPlus | TIC LINKAGE | - |
dc.subject.keywordPlus | NITROGEN | - |
dc.subject.keywordPlus | CLEAVAGE | - |
dc.subject.keywordPlus | ACTIVATION | - |
dc.subject.keywordPlus | REACTIVITY | - |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.