%0 Journal Article
%A Pollock, Christopher
J.
%A Grubel, Katarzyna
%A Holland, Patrick L.
%A DeBeer, Serena
%D 2013
%T Experimentally Quantifying Small-Molecule Bond Activation
Using Valence-to-Core X‑ray Emission Spectroscopy
%U https://acs.figshare.com/articles/journal_contribution/Experimentally_Quantifying_Small_Molecule_Bond_Activation_Using_Valence_to_Core_X_ray_Emission_Spectroscopy/2387011
%R 10.1021/ja3116247.s001
%2 https://ndownloader.figshare.com/files/4026700
%K probe
%K molecule activation
%K N 2 2
%K 0.02 Å
%K N 2 bond activation
%K length
%K XES
%X 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.
%I ACS Publications