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DC Field | Value | Language |
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dc.citation.endPage | 3378 | - |
dc.citation.number | 8 | - |
dc.citation.startPage | 3373 | - |
dc.citation.title | ORGANOMETALLICS | - |
dc.citation.volume | 31 | - |
dc.contributor.author | Blake, Garrett A. | - |
dc.contributor.author | Moerdyk, Jonathan P. | - |
dc.contributor.author | Bielawski, Christopher W. | - |
dc.date.accessioned | 2023-12-22T05:11:13Z | - |
dc.date.available | 2023-12-22T05:11:13Z | - |
dc.date.created | 2020-07-10 | - |
dc.date.issued | 2012-04 | - |
dc.description.abstract | A related series of six-membered carbenes featuring adjoining amino and/or amido groups (i.e, a diaminocarbene, a monoamido-aminocarbene (3), and a a diamidocarbene (6)) were systematically compared using crystallographic, spectroscopic, electro-chemical, and density functional theory methods. The solid-state structure of 3 was found to exhibit inequivalent nitrogen carbon bond lengths (C-carbene-N-amide= 1.395(4) angstrom vs C-carbene-N-amine = 1.323(4) angstrom). Moreover, the C-carbene-N-amide distance was longer than that measured in the solid-state structure of 6 (1.371(3) angstrom), while the C-carbene-N-amine distance was similar to that measured in the solid-state structure of a cyclic alkyl-aminocarbene (1.315(3) angstrom). Iridium complexes of the aforementioned carbenes were also evaluated, and the collected data revealed that the introduction of carbonyl groups to the carbene-containing scaffold had a nearly linear, additive effect on the E-1/2 potential of the carbene-ligated iridium I/II redox couple (+165 mV per carbonyl added) as well as the Tolman electronic parameter value of the corresponding carbene-Ir(CO)(2)Cl complex (ca. 7 cm(-1) per carbonyl added). Beyond attenuated ligand donicity, the introduction of carbonyl groups was found to broaden the chemical reactivity: unlike prototypical N-heterocyclic carbenes, including diaminocarbenes, the monoamido-aminocarbene was found to couple to isonitriles to form the respective ketenimines. | - |
dc.identifier.bibliographicCitation | ORGANOMETALLICS, v.31, no.8, pp.3373 - 3378 | - |
dc.identifier.doi | 10.1021/om3001586 | - |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.scopusid | 2-s2.0-84860330891 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/33144 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/om3001586 | - |
dc.identifier.wosid | 000303071100054 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Tuning the Electronic Properties of Carbenes: A Systematic Comparison of Neighboring Amino versus Amido Groups | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear; Chemistry, Organic | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | N-HETEROCYCLIC CARBENE | - |
dc.subject.keywordPlus | NUCLEOPHILIC CARBENE | - |
dc.subject.keywordPlus | LIGANDS | - |
dc.subject.keywordPlus | CATALYSIS | - |
dc.subject.keywordPlus | N,N&apos | - |
dc.subject.keywordPlus | -DIAMIDOCARBENE | - |
dc.subject.keywordPlus | DIMETHOXYCARBENE | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | CHEMISTRY | - |
dc.subject.keywordPlus | BACKBONE | - |
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