When Werner received a Nobel Prize for his work on complex ions in 1913, he might not have guessed that systematic investigations of these complexes would eventually include the binding of N2 to transition metals. However, the concurrent discovery of artificial nitrogen fixation by Haber led to the wide use of an iron catalyst for the 'Haber Process,' and recent studies on iron-molybdenum nitrogenase imply that iron binding is intimately involved in nitrogen reduction. Given the activity of these large-scale iron catalysts, it is surprising that simple mononuclear Werner-type complexes of iron do not typically weaken the N-N bond of N2. Inspired by the multinuclear nature of the large-scale catalysts, we have developed synthetic iron systems that can weaken and even break the N-N bond of N2. These studies have shown that multiiron active sites are active, particularly when iron cooperates with alkali metals to weaken the N-N bond. This presentation will describe our most recent results on the mechanism of N-N bond cleavage at iron complexes.

Cleavage and functionalization of dinitrogen by multi-iron systems of relevance to the Haber-Bosch process and nitrogenases

246th National Meeting (2013)

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