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DC Field | Value | Language |
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dc.citation.endPage | 11315 | - |
dc.citation.number | 26 | - |
dc.citation.startPage | 11308 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 46 | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Yap, Glenn P. A. | - |
dc.contributor.author | Riordan, Charles G. | - |
dc.date.accessioned | 2023-12-22T09:07:07Z | - |
dc.date.available | 2023-12-22T09:07:07Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2007-12 | - |
dc.description.abstract | A series of high-spin thiolatonickel(II) complexes, [PhTt(tBu)]Ni(SR) (PhTt(tBu) = phenyltris((tert-butylthio) methyl) borate; 2, R = triphenylmethyl; 3, R = pentafluorophenyl; 4, R = phenyl), were synthesized via the reaction of [PhTtBu Ni(NO3) (1) with thiols (RSH) in the presence of triethylamine. The [PhTt(tBu)]]Ni(SR) products were isolated and characterized by various physicochemical measurements including X-ray diffraction analyses. These thiolatonickel(II) complexes have a distorted trigonal pyramidal geometry with somewhat different T values: 0.80 and 0.90 for two crystalline phases of 2, 0.74 for 3, and 0.69 for 4, where tau is a normalized measure of pyramidalization (tau = 0 for tetrahedron, tau = 1 for trigonal pyramid). The electronic absorption spectra display characteristic sulfur-to-nickel(II) charge transfer (CT) bands at 532 nm (7500 M-1 cm(-1)) for 2, 510 nm (4800 M-1 cm(-1)) for 3, and 569 nm (4100 M-1 cm(-1)) for 4. The cyclic voltammograms show a quasi-reversible redox couple at E-1/2 = -1.11 V for 2, and reversible redox couples at E-1/2 = -1.03 V for 3 and E-1/2 = -1.17 V for 4 (vs Fc(+)/Fc). Correlation between the tau value and the CT intensity was observed: the strong CT intensity results from the high tau value, which provides for strong orbital overlap (2 > 3 > 4). Additionally, the CT transition energy correlates with the reduction potential: both the CT transition energy and potential decrease in the order 3 > 2 > 4, consistent with the influence of decreasing electron withdrawing abilities, R = pentafluorophenyl > triphenylmethyl > phenyl. The three thiolatonickel complexes exhibit dramatically different thermal stabilities. Complex 4 is the least stable, undergoing decomposition to [kappa(2)-PhBt(tBu)SPh]Ni(eta(2)-CH2SBut) (5) via net exchange of Ni-SPh and B-CH2SBut groups. | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.46, no.26, pp.11308 - 11315 | - |
dc.identifier.doi | 10.1021/ic701743z | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.scopusid | 2-s2.0-38149054228 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48158 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ic701743z | - |
dc.identifier.wosid | 000251773700045 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Structural, spectroscopic, and electrochemical properties of a series of high-spin thiolatonickel(II) complexes | - |
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 | BLUE COPPER PROTEINS | - |
dc.subject.keywordPlus | MODEL COMPLEXES | - |
dc.subject.keywordPlus | ACTIVE-SITE | - |
dc.subject.keywordPlus | METAL SITES | - |
dc.subject.keywordPlus | COORDINATION | - |
dc.subject.keywordPlus | LIGAND | - |
dc.subject.keywordPlus | TRIS(PYRAZOLYL)BORATE | - |
dc.subject.keywordPlus | REACTIVITY | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | RELEVANCE | - |
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