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rdf:type |
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lifeskim:mentions |
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pubmed:issue |
8
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pubmed:dateCreated |
2007-2-21
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pubmed:abstractText |
A combination of Cu L-edge and S K-edge X-ray absorption data and density functional theory (DFT) calculations has been correlated with 33S electron paramagnetic resonance superhyperfine results to obtain the dipole integral (Is) for the S 1s-->3p transition for the dithiolene ligand maleonitriledithiolate (MNT) in (TBA)2[Cu(MNT)2] (TBA= tetra-n-butylammonium). The results have been combined with the Is of sulfide derived from XPS studies to experimentally obtain a relation between the S 1s-->4p transition energy (which reflects the charge on the S atom, QSmol) and the dipole integral over a large range of QSmol. The results show that, for high charges on S, Is can vary from the previously reported Is values, calculated using data over a limited range of QSmol. A combination of S K-edge and Cu K- and L-edge X-ray absorption data and DFT calculations has been used to investigate the one-electron oxidation of [Cu(MNT)2]2- and [Ni(MNT)2]2-. The conversion of [Cu(MNT)2]2- to [Cu(MNT)2]- results in a large change in the charge on the Cu atom in the molecule (QCumol) and is consistent with a metal-based oxidation. This is accompanied by extensive charge donation from the ligands to compensate the high charge on the Cu in [Cu(MNT)2]- based on the increased S K-edge and decreased Cu L-edge intensity, respectively. In contrast, the oxidation of [Ni(MNT)2]2- to [Ni(MNT)2]- results in a small change in QNimol, indicating a ligand-based oxidation consistent with oxidation of a molecular orbital, psiSOMO (singly occupied molecular orbital), with predominant ligand character.
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pubmed:grant |
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pubmed:commentsCorrections |
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pubmed:language |
eng
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pubmed:journal |
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pubmed:citationSubset |
IM
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pubmed:chemical |
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pubmed:status |
MEDLINE
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pubmed:month |
Feb
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pubmed:issn |
0002-7863
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pubmed:author |
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pubmed:issnType |
Print
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pubmed:day |
28
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pubmed:volume |
129
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
2316-26
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pubmed:dateRevised |
2010-9-14
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pubmed:meshHeading |
pubmed-meshheading:17269767-Copper,
pubmed-meshheading:17269767-Ligands,
pubmed-meshheading:17269767-Models, Chemical,
pubmed-meshheading:17269767-Nickel,
pubmed-meshheading:17269767-Organometallic Compounds,
pubmed-meshheading:17269767-Oxidation-Reduction,
pubmed-meshheading:17269767-Quantum Theory,
pubmed-meshheading:17269767-Sensitivity and Specificity,
pubmed-meshheading:17269767-Spectrum Analysis,
pubmed-meshheading:17269767-Sulfhydryl Compounds,
pubmed-meshheading:17269767-Sulfur,
pubmed-meshheading:17269767-Vibration,
pubmed-meshheading:17269767-X-Rays
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pubmed:year |
2007
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pubmed:articleTitle |
Sulfur K-edge X-ray absorption spectroscopy as a probe of ligand-metal bond covalency: metal vs ligand oxidation in copper and nickel dithiolene complexes.
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pubmed:affiliation |
Department of Chemistry, Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center, Stanford University, Stanford, California 94309, USA.
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pubmed:publicationType |
Journal Article,
Research Support, U.S. Gov't, Non-P.H.S.,
Research Support, Non-U.S. Gov't,
Research Support, N.I.H., Extramural
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