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K? mainline X-ray emission spectroscopy as an experimental probe of metal-ligand covalency.

ABSTRACT: The mainline feature in metal K? X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of K? mainline XES. Ligand field expressions are derived that describe the behavior of K? mainlines for first row transition metals with any d(n) count, allowing for a detailed analysis of the factors governing mainline shape. Further, due to limitations associated with existing computational approaches, we have developed a new methodology for calculating K? mainlines using restricted active space configuration interaction (RAS-CI) calculations. This approach eliminates the need for empirical parameters and provides a powerful tool for investigating the effects that chemical environment exerts on the mainline spectra. On the basis of a detailed analysis of the intermediate and final states involved in these transitions, we confirm the known sensitivity of K? mainlines to metal spin state via the 3p-3d exchange coupling. Further, a quantitative relationship between the splitting of the K? mainline features and the metal-ligand covalency is established. Thus, this study furthers the quantitative electronic structural information that can be extracted from K? mainline spectroscopy.

SUBMITTER: Pollock CJ

PROVIDER: S-EPMC4091279 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

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Kβ mainline X-ray emission spectroscopy as an experimental probe of metal-ligand covalency.

Pollock Christopher J CJ Delgado-Jaime Mario Ulises MU Atanasov Mihail M Neese Frank F DeBeer Serena S

Journal of the American Chemical Society 20140620 26

The mainline feature in metal Kβ X-ray emission spectroscopy (XES) has long been recognized as an experimental marker for the spin state of the metal center. However, even within a series of metal compounds with the same nominal oxidation and spin state, significant changes are observed that cannot be explained on the basis of overall spin. In this work, the origin of these effects is explored, both experimentally and theoretically, in order to develop the chemical information content of Kβ main ...[more]

PMID: 24914450

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Project description:Nitrogen K-edge X-ray absorption spectra (XAS) were obtained for 19 transition metal complexes bearing bipyridine, ethylenediamine, ammine, and nitride ligands. Time-dependent density functional theory (TDDFT) and DFT/restricted open configuration interaction singles (DFT/ROCIS) calculations were found to predict relative N K-edge XAS peak energies with good fidelity to experiment. The average difference (|ΔE|) between experimental and linear corrected calculated energies were found to be 0.55 ± 0.05 eV and 0.46 ± 0.04 eV, respectively, using the B3LYP hybrid density functional and scalar relativistically recontracted ZORA-def2-TZVP(-f) basis set. Deconvolution of these global correlations into individual N-donor ligand classes gave improved agreement between experiment and theory with |ΔE| less than 0.4 eV for all ligand classes in the case of DFT/ROCIS. In addition, calibration method-dependent values for the N 1s → 2p radial dipole integral of 25.4 ± 1.7 and 26.8 ± 1.9 are obtained, affording means to estimate the nitrogen 2p character in unfilled frontier molecular orbitals. For the complexes studied, nitrogen covalency values correlate well to those calculated by hybrid DFT with an R 2 = 0.92 ± 0.01. Additionally, as a test case, a well-characterized PNP ligand framework (PNP = N[2-P(CHMe2)2-4-methylphenyl]2 1-) coordinated to NiII is investigated for its ability to act as a redox non-innocent ligand. Upon oxidation of (PNP)NiCl with [FeCp2](OTf) to its radical cation, [(PNP)NiCl](OTf) (OTf = triflate), a new low-energy feature emerges in the N K-edge XAS spectra. This feature is assigned as N 1s to a PNP-localized acceptor orbital exhibiting 27 ± 2% N 2p aminyl radical character, obtained using the aforementioned nitrogen covalency calibration. Combined, these data showcase a direct spectroscopic means of identifying redox-active N-donor ligands and also estimating nitrogen 2p covalency of frontier molecular orbitals in transition metal complexes.

Dataset Information

K? mainline X-ray emission spectroscopy as an experimental probe of metal-ligand covalency.

Publications

Kβ mainline X-ray emission spectroscopy as an experimental probe of metal-ligand covalency.

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