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DC Field | Value | Language |
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dc.citation.endPage | 6445 | - |
dc.citation.number | 16 | - |
dc.citation.startPage | 6435 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 45 | - |
dc.contributor.author | Rohde, Jan-Uwe | - |
dc.contributor.author | Stubna, Audria | - |
dc.contributor.author | Bominaar, Emile L. | - |
dc.contributor.author | Munck, Eckard | - |
dc.contributor.author | Nam, Wonwoo | - |
dc.contributor.author | Que, Lawrence, Jr. | - |
dc.date.accessioned | 2023-12-22T09:43:36Z | - |
dc.date.available | 2023-12-22T09:43:36Z | - |
dc.date.created | 2015-07-03 | - |
dc.date.issued | 2006-08 | - |
dc.description.abstract | Treatment of [Fe-IV(O)(TPA)(NCMe)](CF3SO3)(2) [TPA, N, N, N- tris(2-pyridylmethyl) amine] with 3 equiv of NR4X (X = CF3CO2, Cl, or Br) in MeCN at -40 degrees C affords a series of metastable [FeIV(O)(TPA)(X)](+) complexes. Some characteristic features of the S = 1 oxoiron(IV) unit are quite insensitive to the ligand substitution in the equatorial plane, namely, the Fe-O distances (1.65-1.66 angstrom), the energy (similar to 7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the Mossbauer isomer shifts (0.01-0.06 mm center dot s(-1)) and quadrupole splittings (0.92-0.95 mm, s(-1)). The coordination of the anionic X ligand, however, is evidenced by red shifts of the characteristic near-IR ligand-field bands (720-800 nm) and spectroscopic observation of the bound anion by F-19 NMR for X = CF3CO2 and by EXAFS analysis for X = Cl (r(Fe-Cl) = 2.29 angstrom) and Br (r(Fe-Br) = 2.43 angstrom). Density functional theory calculations yield Mossbauer parameters and bond lengths in good agreement with the experimental data and produce excited-state energies that follow the trend observed in the ligand-field bands. Despite mitigating the high effective charge of the iron(IV) center, the substitution of the MeCN ligand with monoanionic ligands X- decreases the thermal stability of [FeIV(O)(TPA)](2+) complexes. These anion-substituted complexes model the cis-X-Fe-IV = O units proposed in the mechanisms of oxygen-activating nonheme iron enzymes | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.45, no.16, pp.6435 - 6445 | - |
dc.identifier.doi | 10.1021/ic060740u | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.scopusid | 2-s2.0-33748255753 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/11977 | - |
dc.identifier.url | http://pubs.acs.org/doi/abs/10.1021/ic060740u | - |
dc.identifier.wosid | 000239394300049 | - |
dc.language | 영어 | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | Nonheme oxoiron(IV) complexes of tris(2-pyridylmethyl) amine with cis-monoanionic ligands | - |
dc.type | Article | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | ALPHA-KETOGLUTARATE DIOXYGENASE | - |
dc.subject.keywordPlus | FE-IV=O COMPLEX | - |
dc.subject.keywordPlus | SPECTROSCOPIC CHARACTERIZATION | - |
dc.subject.keywordPlus | (MU-OXO)DIIRON(III) COMPLEXES | - |
dc.subject.keywordPlus | ELECTRONIC-STRUCTURE | - |
dc.subject.keywordPlus | OXYGEN ACTIVATION | - |
dc.subject.keywordPlus | ESCHERICHIA-COLI | - |
dc.subject.keywordPlus | DIIRON COMPLEXES | - |
dc.subject.keywordPlus | ACTIVE-SITE | - |
dc.subject.keywordPlus | PRE-EDGE | - |
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