title: Experimentally quantifying small-molecule bond activation using valence-to-core X-ray emission spectroscopy.
abstract: This work establishes the ability of valence-to-core X-ray emission spectroscopy (XES) to serve as a direct probe of N2 bond activation. A systematic series of iron-N2 complexes has been experimentally investigated and the energy of a valence-to-core XES peak was correlated with N-N bond length and stretching frequency. Computations demonstrate that, in a simple one-electron picture, this peak arises from the N2 2s2s σ* orbital, which becomes less antibonding as the N-N bond is weakened and broken. Changes as small as 0.02 Å in the N-N bond length may be distinguished using this approach. The results thus establish valence-to-core XES as an effective probe of small molecule activation, which should have broad applicability in transition-metal mediated catalysis.
authors.affiliation: Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, D45470 Mülheim an der Ruhr, Germany.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Pollock
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Grubel
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland
authors.forename: Serena
authors.initials: S
authors.lastname: DeBeer
mesh_terms: D058085:Iron Compounds / Q000737:chemistry*; D008958:Models, Molecular; D009584:Nitrogen / Q000737:chemistry*; D011789:Quantum Theory; D054852:Small Molecule Libraries / Q000737:chemistry*; D013052:Spectrometry, X-Ray Emission / Q000379:methods*
chemical_list: D058085:Iron Compounds; D054852:Small Molecule Libraries; D009584:Nitrogen