NDLI: Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal

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Chemical Science Vol - 6 Issue - 3

Chemical Science Vol - 6 Issue - 2

Chemical Science Vol -5

Chemical Science Vol -4

Chemical Science Vol -3

Chemical Science Vol -2

Chemical Science Vol -1

Re-evaluating the Cu K pre-edge XAS transition in complexes with covalent metal–ligand interactions

Content Provider	Royal Society of Chemistry (RSC)
Author	Sproules, Stephen Tomson, Neil C. Wieghardt, Karl Warren, Timothy H. DeBeer, Serena Dai, Xuliang Williams, Kamille D.
Copyright Year	2015
Abstract	Three [Me2NN]Cu(η2-L2) complexes (Me2NN = HC[C(Me)NAr]2; L2 = PhNO (2), (3), PhCHCH2 (4); Ar = 2,6-Me2-C6H3; ArF = 3,5-(CF3)2-C6H3) have been studied by Cu K-edge X-ray absorption spectroscopy, as well as single- and multi-reference computational methods (DFT, TD-DFT, CASSCF, MRCI, and OVB). The study was extended to a range of both known and theoretical compounds bearing 2p-element donors as a means of deriving a consistent view of how the pre-edge transition energy responds in systems with significant ground state covalency. The ground state electronic structures of many of the compounds under investigation were found to be strongly influenced by correlation effects, resulting in ground state descriptions with majority contributions from a configuration comprised of a Cu(II) metal center anti-ferromagentically coupled to radical anion O2, PhNO, and ligands. In contrast, the styrene complex 4, which displays a Cu K pre-edge transition despite its formal d10 electron configuration, exhibits what can best be described as a Cu(I):(styrene)0 ground state with strong π-backbonding. The Cu K pre-edge features for these complexes increase in energy from 1 to 4, a trend that was tracked to the percent Cu(II)-character in the ground state. The unexpected shift to higher pre-edge transition energies with decreasing charge on copper (QCu) contributed to an assignment of the pre-edge features for these species as arising from metal-to-ligand charge transfer instead of the traditional Cu1s → Cu3d designation.
Starting Page	2474
Ending Page	2487
Page Count	14
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	6
Issue Number	4
Journal	Chemical Science
DOI	10.1039/c4sc03294b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Absorption spectroscopy Metal K-edge Multireference configuration interaction Styrene X-ray absorption spectroscopy Electron configuration Copper Radical ion
Content Type	Text
Resource Type	Article
Subject	Chemistry

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