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DC Field | Value | Language |
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dc.citation.endPage | 6049 | - |
dc.citation.number | 24 | - |
dc.citation.startPage | 6042 | - |
dc.citation.title | ORGANOMETALLICS | - |
dc.citation.volume | 26 | - |
dc.contributor.author | Khramov, Dirnitri M. | - |
dc.contributor.author | Lynch, Vincent M. | - |
dc.contributor.author | Bielawski, Christopher W. | - |
dc.date.accessioned | 2023-12-22T09:07:56Z | - |
dc.date.available | 2023-12-22T09:07:56Z | - |
dc.date.created | 2020-07-13 | - |
dc.date.issued | 2007-11 | - |
dc.description.abstract | The ability of N-heterocyclic carbenes (NHCs) to participate in pi-back-bonding interactions was evaluated in a range of transition metal complexes. Rh chloride complexes containing a systematic series of various 1,3-dimethyl-4,5-disubstituted-imidazol-2-ylidenes and either 1,5-cyclooctadiene (cod) or two carbon monoxide ligands were synthesized (i.e., (NHC)RhCl(cod) and (NHC)RhCl(CO)(2), respectively) and studied using H-1 NMR and IR spectroscopies. In the former series, the H-1 NMR chemical shifts of the signals attributable to the olefin trans to the NHC ligand were found to shift downfield by up to 0.17 ppm as the pi-acidity of the substituents on the 4,5-positions increased (i.e., H -> Cl -> CN). Similarly, in the latter series, the IR stretching frequencies of the carbonyl groups trans to the NHC ligands were found to increase by 11 +/- 0.5 cm(-1) as it-acidity increased over the same series. Using the nitrile group as a diagnostic handle, the CN stretching frequency of (1,3-dimethyl-4,5-dicyanoimidazol-2-ylidene)(cod)RhCl was found to be 4 +/- 0.5 cm(-1) higher than 1,3-dimethyl-4,5-dicyanoimidazol-2-ylidene)(CO)(2)RhCl, a more pi-acidic analogue. X-ray analysis of the aforementioned series of (NHC)(cod)RhCl complexes indicated changes in N-C-carbene bond lengths that were consistent with greater pi-donation from complexes containing 4,5-dihydroimidazol-2-ylidene relative to the their 4,5-dicyano analogues. Collectively, these results suggest not only that imidazol-2-ylidenes are capable of pi-back-bonding but that this interaction may be tuned by changing the pi-acidity of the substituents on the imidazole ring. | - |
dc.identifier.bibliographicCitation | ORGANOMETALLICS, v.26, no.24, pp.6042 - 6049 | - |
dc.identifier.doi | 10.1021/om700591z | - |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.scopusid | 2-s2.0-36749009530 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/33291 | - |
dc.identifier.url | https://pubs.acs.org/doi/abs/10.1021/om700591z | - |
dc.identifier.wosid | 000250975200036 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | N-heterocyclic carbene-transition metal complexes: Spectroscopic and crystallographic analyses of pi-back-bonding interactions | - |
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 | CHAIN ORGANOMETALLIC POLYMERS | - |
dc.subject.keywordPlus | MAIN-GROUP ELEMENTS | - |
dc.subject.keywordPlus | RUCL CP-ASTERISK | - |
dc.subject.keywordPlus | NUCLEOPHILIC CARBENES | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | COPPER(I) COMPLEXES | - |
dc.subject.keywordPlus | ETA(5)-C5ME5 MOIETY | - |
dc.subject.keywordPlus | COUPLING REACTIONS | - |
dc.subject.keywordPlus | LIGAND PROPERTIES | - |
dc.subject.keywordPlus | MULTIPLE BONDS | - |
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