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DC Field | Value | Language |
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dc.citation.endPage | 6544 | - |
dc.citation.number | 14 | - |
dc.citation.startPage | 6535 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 49 | - |
dc.contributor.author | Van Heuvelen, Katherine M. | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Dingee, Timothy | - |
dc.contributor.author | Riordan, Charles G. | - |
dc.contributor.author | Brunold, Thomas C. | - |
dc.date.accessioned | 2023-12-22T06:07:30Z | - |
dc.date.available | 2023-12-22T06:07:30Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2011-07 | - |
dc.description.abstract | The electronic structures of a series of high-spin Ni(II)-thiolate complexes of the form [PhTt(tBu)]Ni(SR) (R = CPh3, 2; C6F5, 3; C6H5, 4; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate) have been characterized using a combined spectroscopic and computational approach. Resonance Raman (rR) spectroscopic data reveal that the nu(Ni-SR) vibrational feature occurs between 404 and 436 cm(-1) in these species. The corresponding rR excitation profiles display a striking de-enhancement behavior because of interference effects involving energetically proximate electronic excited states. These data were analyzed in the framework of time-dependent Heller theory to obtain quantitative insight into excited state nuclear distortions. The electronic absorption and magnetic circular dichroism spectra of 2-4 are characterized by numerous charge transfer (CT) transitions. The dominant absorption feature, which occurs at similar to 18,000 cm(-1) in all three complexes, is assigned as a thiolate-to-Ni CT transition involving molecular orbitals that are of pi -symmetry with respect to the Ni-S bond, reminiscent of the characteristic absorption feature of blue copper proteins. Density functional theory computational data provide molecular orbital descriptions for 2-4 and allow for detailed assignments of the key spectral features. A comparison of the results obtained in this study to those reported for similar Ni-thiolate species reveals that the supporting ligand plays a secondary role in determining the spectroscopic properties, as the electronic structure is primarily determined by the metal -thiolate bonding interaction. | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.49, no.14, pp.6535 - 6544 | - |
dc.identifier.doi | 10.1021/ic100362q | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48141 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ic100362q | - |
dc.identifier.wosid | 000279621200039 | - |
dc.language | 영어 | - |
dc.publisher | American Chemical Society (ACS) | - |
dc.title | Spectroscopic and Computational Studies of a Series of High-Spin Ni(II) Thiolate Complexes | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.relation.journalResearchArea | 000279621200039 | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | COENZYME-M-REDUCTASE | - |
dc.subject.keywordPlus | ACTIVE-SITE | - |
dc.subject.keywordPlus | SUPEROXIDE-DISMUTASE | - |
dc.subject.keywordPlus | RAMAN-SCATTERING | - |
dc.subject.keywordPlus | CORRELATION-ENERGY | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | MODEL COMPLEXES | - |
dc.subject.keywordPlus | EXCITED-STATES | - |
dc.subject.keywordPlus | HARTREE-FOCK | - |
dc.subject.keywordPlus | METAL SITES | - |
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