X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(Hbuea)FeX] (X = S, O, OH): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes.
Iron L-edge, iron L-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [FeHbuea(X)] (X = S, O, OH). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 30; pp. 9825 - 9834 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
8/2/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=21862022&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 21862022 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/2/2006 vid: 128 iid: 30 pid: 997 pub: American Chemical Society artinfo: ui: 21862022 10.1021/ja061618x ppf: 9825 ppct: 9 formats: tig: atl: X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(Hbuea)FeX] (X = S, O, OH): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes. aug: au: Dey, Abhishek Hocking, Rosalie K. Larsen, Peter Borovik, Andrew S. Hodgson, Keith O. Hedman, Britt Solomon, Edward I. affil: Department of Chemistry, Stanford University, Stanford, California 94305 Stanford Synchrotron Radiation Laboratory, SLAC, Stanford University, Menlo Park, California 94025 Department of Chemistry, Kansas University, Lawrence, Kansas 66045 su: X-ray spectroscopy Spectrum analysis Density functionals Functional analysis Ligand binding (Biochemistry) Biochemistry sug: subj: X-ray spectroscopy Spectrum analysis Density functionals Functional analysis Ligand binding (Biochemistry) Biochemistry ab: Iron L-edge, iron L-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [FeHbuea(X)] (X = S, O, OH). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metalligand bonding and to evaluate the effects of H-bonding in FeO vs FeS complexes. It was found that the FeO bond, while less covalent, is stronger than the FeS bond. This dominantly reflects the larger ionic contribution to the FeO bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the FeO bond. These results were extended to consider an FeO complex with the same ligand environment. It was found that hydrogen bonding to FeO is less energetically favorable than that to FeO, which reflects the highly covalent nature of the FeO bond. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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