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Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS
Journal article   Peer reviewed

Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS

Kyounghoon Lee, Anastasia V Blake, Courtney M Donahue, Kyle D Spielvogel, Brian J Bellott and Scott R Daly
Angewandte Chemie (International ed.), Vol.58(36), pp.12451-12455
09/02/2019
DOI: 10.1002/anie.201905635
PMID: 31271502

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Abstract

Bond distance is a common structural metric used to assess changes in metal–ligand bonds, but it is not clear how sensitive changes in bond distances are with respect to changes in metal–ligand covalency. Here we report ligand K‐edge XAS studies on Ni and Pd complexes containing different phosphorus(III) ligands. Despite the large number of electronic and structural permutations, P K‐edge pre‐edge peak intensities reveal a remarkable correlation that spectroscopically quantifies the linear interdependence of covalent M−P σ bonding and bond distance. Cl K‐edge studies conducted on many of the same Ni and Pd compounds revealed a poor correlation between M−Cl bond distance and covalency, but a strong correlation was established by analyzing Cl K‐edge data for Ti complexes with a wider range of Ti−Cl bond distances. Together these results establish a quantitative framework to begin making more accurate assessments of metal–ligand covalency using bond distances from readily‐available crystallographic data. Ligand K‐edge X‐ray absorption spectroscopy studies were used to quantify the interdependence of metal–ligand covalency and bond distance in metal–phosphorus and metal–chloride bonds. The results establish a quantitative framework to assess changes in metal–ligand covalency using bond distances from readily available crystallographic data.
 bond distance covalency ionic radii ligand K-edge XAS metal–ligand bond

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