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Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti–O–(C, Si, Ge) Complexes
journal contribution
posted on 2016-12-13, 00:00 authored by Charles S. Spanjers, Pascal Guillo, T. Don Tilley, Michael J. Janik, Robert M. RiouxX-ray
absorption near-edge structure (XANES) is a common technique for elucidating
oxidation state and first shell coordination geometry in transition
metal complexes, among many other materials. However, the structural
information obtained from XANES is often limited to the first coordination
sphere. In this study, we show how XANES can be used to differentiate
between C, Si, and Ge in the second coordination shell of Ti–O–(C,
Si, Ge) molecular complexes based on differences in their Ti K-edge
XANES spectra. Experimental spectra were compared with theoretical
spectra calculated using density functional theory structural optimization
and ab initio XANES calculations. The unique features for second shell
C, Si, and Ge present in the Ti K pre-edge XANES are attributed to
the interaction between the Ti center and the O–X (X = C, Si,
or Ge) antibonding orbitals.
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Keywords
antibonding orbitalsSecond Shell Coordinationshell CExperimental spectraTi centershell coordination geometryab initio XANES calculationsComplexes X-ray absorption near-edge structureTransition Metal SpeciesSicoordination sphereelucidating oxidation stateTi K-edge XANES spectraTheoretical XANESGetransition metal complexesTi K pre-edge XANEScoordination shell
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