X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes.
We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and t...
| Publicado en: | Journal of the American Chemical Society Vol. 131; no. 36; pp. 13161 - 13168 |
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| Autores principales: | , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
9/16/2009
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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=44466071&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 44466071 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: 9/16/2009 vid: 131 iid: 36 pid: 997 pub: American Chemical Society artinfo: ui: 44466071 10.1021/ja808526m ppf: 13161 ppct: 7 formats: tig: atl: X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes. aug: au: Smolentsev, Grigory Soldatov, Alexander V. Messinger, Johannes Merz, Kathrin Weyhermüller, Thomas Bergmann, Uwe Pushkar, Yulia Junko, Junko Yachandra, Vittal K. Glatzel, Pieter affil: Faculty of Physics and Research Center for Nanoscale Structure of Matter, Southern Federal University, 344090 Rostov-on-Don, Russia Max-Planck Institute for Bioinorganic Chemistry, Stiftstr. 34-36, 45470 Mülheim, Germany Department of Chemistry, Umeå University, S-90187 Umeå, Sweden Stanford Synchrotron Radiation Lightsource, P.O. Box 20450 Stanford, California 94309 Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 Department of Physics, Purdue University, West Lafayette, Indiana 47907 European Synchrotron Radiation Facility, 6, rue Jules Horowitz, 38043 Grenoble, France su: X-ray spectroscopy Ligands (Chemistry) Manganese Density functionals Chemical research sug: subj: X-ray spectroscopy Ligands (Chemistry) Manganese Density functionals Chemical research ab: We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion is level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O…), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(HO)], [Mn(HO)OH], and [Mn(HO)NH]. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn ion in water and three Mn coordination complexes, namely [LMn(acac)N]BPh, [LMn(BOPh)(ClO)], and [LMn(acac)N]BPh, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and BOPh represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2009 holdings: @attributes: islocal: N |
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