Aug 12, 2009

X-ray emission spectroscopy to study ligand valence orbitals in Mn coordination complexes

Journal of the American Chemical Society
Grigory SmolentsevPieter Glatzel

Abstract

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 1s 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(H(2)O)(6)](2+), [Mn(H(2)O)(5)OH](+), and [Mn(H(2)O)(5)NH(3)](2+). An application of the method, with comparison between theory and experiment, is presented for the solvated Mn(2+) ion in water and three Mn coordination complexes, namely [LMn(acac)N(3)]BPh(4), [LMn(B(2)O(3)Ph(2))(ClO(4))], and [LMn(acac)N]BPh(4), where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands fo...Continue Reading

Mentioned in this Paper

Plain X-ray
Diphenyl
1,4,7-trimethyl-1,4,7-triazacyclononane
Radiographic Imaging Procedure
Diphenyl (fungicide)
Ligands Activity
ACACA wt Allele
Ligands
Coordination Complexes
Wavelength Dispersive X-Ray Spectrometry

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