There are no files associated with this item.
Full metadata record
DC Field | Value | Language |
---|---|---|
dc.citation.endPage | 13264 | - |
dc.citation.number | 36 | - |
dc.citation.startPage | 13251 | - |
dc.citation.title | DALTON TRANSACTIONS | - |
dc.citation.volume | 42 | - |
dc.contributor.author | Varnado, C. Daniel, Jr. | - |
dc.contributor.author | Rosen, Evelyn L. | - |
dc.contributor.author | Collins, Mary S. | - |
dc.contributor.author | Lynch, Vincent M. | - |
dc.contributor.author | Bielawski, Christopher W. | - |
dc.date.accessioned | 2023-12-22T04:18:03Z | - |
dc.date.available | 2023-12-22T04:18:03Z | - |
dc.date.created | 2020-03-04 | - |
dc.date.issued | 2013 | - |
dc.description.abstract | A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst. | - |
dc.identifier.bibliographicCitation | DALTON TRANSACTIONS, v.42, no.36, pp.13251 - 13264 | - |
dc.identifier.doi | 10.1039/c3dt51278a | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.scopusid | 2-s2.0-84882771556 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/31505 | - |
dc.identifier.url | https://pubs.rsc.org/en/content/articlelanding/2013/DT/c3dt51278a#!divAbstract | - |
dc.identifier.wosid | 000323274800059 | - |
dc.language | 영어 | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | Synthesis and study of olefin metathesis catalysts supported by redox-switchable diaminocarbene[3]ferrocenophanes | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Inorganic & Nuclear | - |
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 | RUTHENIUM-INDENYLIDENE COMPLEXES | - |
dc.subject.keywordPlus | TRANSITION-METAL-COMPLEXES | - |
dc.subject.keywordPlus | CROSS-COUPLING REACTIONS | - |
dc.subject.keywordPlus | FACE DONOR PROPERTIES | - |
dc.subject.keywordPlus | ACTIVE LIGAND | - |
dc.subject.keywordPlus | OXIDATION-STATE | - |
dc.subject.keywordPlus | SUZUKI-MIYAURA | - |
dc.subject.keywordPlus | ACYCLIC DIAMINOCARBENE | - |
dc.subject.keywordPlus | ELECTRONIC-PROPERTIES | - |
Items in Repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Tel : 052-217-1404 / Email : scholarworks@unist.ac.kr
Copyright (c) 2023 by UNIST LIBRARY. All rights reserved.
ScholarWorks@UNIST was established as an OAK Project for the National Library of Korea.