Nitrogen Fixation

Christiansen, J. A.; Dean, Dennis R.

doi:10.1002/047120918x.emb1004

Cited by 1 publication

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“…27, 28 The reactivity patterns of nitrogenase variants with changes in the amino acids near the FeMoco imply that N 2 binds to one or more of the iron atoms on a four-iron face of the FeMoco. 29, 30 It is notable that multimetallic iron sites are important in both natural and industrial N 2 fixation.…”

Section: Introductionmentioning

confidence: 99%

Multimetallic cooperativity in activation of dinitrogen at iron–potassium sites

et al. 2014

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The reaction of soluble iron-oxygen-potassium assemblies with N2 gives insight into the mechanisms of multimetallic N2 coordination. We report a series of very electron-rich three-coordinate, β-diketiminate-supported iron(I) phenoxide complexes, which are metastable but have been characterized under Ar by both crystallography and solution methods. Both monomeric and dimeric Fe-OPh-K compounds have been characterized, and their iron environments are very similar in the solid and solution states. In the dimer, potassium ions hold together the phenoxide oxygens and aryl rings of the two halves, to give a flexible diiron core. The reactions of the monomeric and dimeric iron(I) compounds with N2 are surprisingly different: the mononuclear iron(I) complexes give no reaction with N2, but the dimeric Fe2K2 complex reacts rapidly to give a diiron-N2 product. Computational studies show that the key to the rapid N2 reaction of the dimer is the preorganization of the two iron atoms. Thus, cooperation between Fe (which weakens the N-N bond) and K (which orients the Fe atoms) can be used to create a low-energy pathway for N2 reactions.

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