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

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• 作者：Christopher J. Pollock ; Katarzyna Grubel ; Patrick L. Holland ; Serena DeBeer
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：August 14, 2013
• 年：2013
• 卷：135
• 期：32
• 页码：11803-11808
• 全文大小：386K
• 年卷期：v.135,no.32(August 14, 2013)
• ISSN：1520-5126

文摘

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鈥揘 bond length and stretching frequency. Computations demonstrate that, in a simple one-electron picture, this peak arises from the N₂ 2s2s 蟽* orbital, which becomes less antibonding as the N鈥揘 bond is weakened and broken. Changes as small as 0.02 脜 in the N鈥揘 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.