Katarzyna Grubel - Experimentally Quantifying Small Molecule Bond Activation Using Valence-to-Core X-ray Emission Spectroscopy

Version 1

      Publication Details (including relevant citation   information):

      Pollock, C.; Grubel, K.; Holland, P. L.; DeBeer, S. Journal   of American Chemical Society
      2013, 135, 11803–11808.


        Abstract Image 

        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.  

      Address (URL): http://pubs.acs.org/doi/abs/10.1021/ja3116247