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Issue 1, 2014
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Multimetallic cooperativity in activation of dinitrogen at iron–potassium sites

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Abstract

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.

Graphical abstract: Multimetallic cooperativity in activation of dinitrogen at iron–potassium sites

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Publication details

The article was received on 04 Sep 2013, accepted on 14 Oct 2013 and first published on 15 Oct 2013


Article type: Edge Article
DOI: 10.1039/C3SC52487F
Chem. Sci., 2014,5, 267-274

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    Multimetallic cooperativity in activation of dinitrogen at iron–potassium sites

    K. P. Chiang, S. M. Bellows, W. W. Brennessel and P. L. Holland, Chem. Sci., 2014, 5, 267
    DOI: 10.1039/C3SC52487F

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