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Assignment of Pre-edge Features in the Ru K-edge X-ray Absorption Spectra of Organometallic Ruthenium Complexes.

TitleAssignment of Pre-edge Features in the Ru K-edge X-ray Absorption Spectra of Organometallic Ruthenium Complexes.
Publication TypeJournal Article
Year of Publication2008
AuthorsGetty, K, Delgado-Jaime, MUlises, Kennepohl, P
JournalInorg. Chim. Acta
Volume361
Pagination1059
ISSN0020-1693
KeywordsDFT, OLEFIN METATHESIS, XAS
Abstract

The nature of the lowest energy bound-state transition in the Ru K-edge X-ray Absorption Spectra for a series of Grubbs-type ruthenium complexes was investigated. The pre-edge feature was unambiguously assigned as resulting from formally electric dipole forbidden Ru 4d<–1s transitions. The intensities of these transitions are extremely sensitive to the ligand environment and the symmetry of the metal centre. In centrosymmetric complexes the pre-edge is very weak since it is limited by the weak electric quadrupole intensity mechanism. By contrast, upon breaking centrosymmetry, Ru 5p-4d mixing allows for introduction of electric dipole allowed character resulting in a dramatic increase in the pre-edge intensity. The information content of this approach is explored as it relates to complexes of importance in olefin metathesis and its relevance as a tool for the study of reactive intermediates.

URLhttp://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=2819416&tool=pmcentrez&rendertype=abstract
DOI10.1016/j.ica.2007.07.029