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DC Field | Value | Language |
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dc.citation.endPage | 2580 | - |
dc.citation.number | 5 | - |
dc.citation.startPage | 2564 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 52 | - |
dc.contributor.author | Kelley, Matthew R. | - |
dc.contributor.author | Rohde, Jan-Uwe | - |
dc.date.accessioned | 2023-12-22T04:10:12Z | - |
dc.date.available | 2023-12-22T04:10:12Z | - |
dc.date.created | 2014-08-28 | - |
dc.date.issued | 2013-03 | - |
dc.description.abstract | A series of seven [Ir{ArNC(NR2)NAr}(cod)] complexes (1a-1g; where R = Me or Et; Ar = Ph, 4-MeC6H4, 4-MeOC 6H4, 2,6-Me2C6H3, or 2,6-iPr2C6H3; and cod = 1,5-cyclooctadiene) were synthesized by two different methods from the neutral guanidines, ArN-C(NR2)NHAr, using either MeLi and [{Ir(cod)} 2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe) 2]. Reaction of 1a-1g with CO produced the corresponding [Ir{ArNC(NR2)NAr}(CO)2] complexes (2a-2g), which were characterized by NMR and solution- and solid-state IR spectroscopy. Complexes 1b (R = Et, Ar = Ph), 1d (R = Et, Ar = 4-MeC6H4), 1f (R = Me, Ar = 2,6-Me2C6H3), and 2b (R = Et, Ar = Ph) were characterized by X-ray crystallography as mononuclear complexes with a guanidinato-κ2N,N′ ligand and a cod or two CO ligands coordinated to the Ir center in a distorted square-planar environment. On the basis of the CO stretching frequencies of 2a-2g [avg. νCO (n-pentane) = 2016-2019 cm-1] and the alkene 13C chemical shifts of 1a-1g [δ(13CC-C) = 58.7-61.0 ppm], the donor strength of the guanidinato ligands was evaluated and compared to that of related monoanionic ligands. Reaction of 1a-1g in solution with O2 at 20 C afforded (alkene)peroxoiridium(III) intermediates, [Ir{ArNC(NR 2)NAr}(cod)(O2)] (3). The steric properties of the supporting ligand play a decisive role in O2 binding in that complexes without ortho substituents react largely irreversibly with O 2 (1a-1e; where Ar = Ph, 4-MeC6H4 or 4-MeOC6H4), whereas complexes with ortho substituents exhibit fully reversible O2 binding (1f and 1g; where Ar = 2,6-Me2C6H3 or 2,6-iPr 2C6H3). Complexes 3a-3f were characterized by 1H NMR and IR spectroscopy (νOO = 857-872 cm -1). Decay of the new intermediates and subsequent reaction with cod produced 4-cycloocten-1-one and the respective IrI precursor. | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.52, no.5, pp.2564 - 2580 | - |
dc.identifier.doi | 10.1021/ic302570s | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.scopusid | 2-s2.0-84874591635 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/5727 | - |
dc.identifier.url | http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=84874591635 | - |
dc.identifier.wosid | 000315763300041 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Guanidinato Complexes of Iridium: Ligand-Donor Strength, O2 Reactivity, and (Alkene)peroxoiridium(III) Intermediates | - |
dc.type | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | N-HETEROCYCLIC CARBENES | - |
dc.subject.keywordPlus | TRANSITION-METAL-COMPLEXES | - |
dc.subject.keywordPlus | OXIDATION-STATE METALLACYCLES | - |
dc.subject.keywordPlus | SPIN-ECHO MEASUREMENTS | - |
dc.subject.keywordPlus | HYDROGEN-ATOM TRANSFER | - |
dc.subject.keywordPlus | X-RAY STRUCTURES | - |
dc.subject.keywordPlus | MOLECULAR-OXYGEN | - |
dc.subject.keywordPlus | DIOXYGEN COMPLEXES | - |
dc.subject.keywordPlus | ORGANOMETALLIC CHEMISTRY | - |
dc.subject.keywordPlus | CATALYZED OXIDATION | - |
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