Cleavage of N-N multiple bonds is important in agriculture, organic synthesis, and energy storage.  There are few systems that can cleave the N-N multiple bonds, including the nitrogenase enzyme and the heterogeneous catalyst in the Haber-Bosch process, which both use iron active sites.  The work reported here describes an example of N-N multiple bond cleavage in well-characterized iron complexes, which help to understand the mechanism of NN bond cleavage.  The addition of azobenzene to [LMe,Et2Fe]2 or [LMe,Et2FeH]2 resulted in the cleavage of the N=N bond to form a bis(�-imido)diiron complex.  This reaction has been studied using DFT and experimental kinetics to elucidate the mechanism of H2 reductive elimination and N=N bond cleavage.  Preliminary results suggest that the binding of azobenzene [LMe,Et2FeH]2 is necessary to drive H2 loss.

N=N bond cleavage of azobenzene by low-valent iron

243rd National Meeting (2012)

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