Multimetallic Cooperativity in Activation of Dinitrogen at Iron-Potassium Sites.

The reaction of soluble iron-oxygen-potassium assemblies with N gives insight into the mechanisms of multimetallic N 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 N are surprisingly different: the mononuclear iron(I) complexes give no reaction with N, but the dimeric FeK complex reacts rapidly to give a diiron-N product. Computational studies show that the key to the rapid N 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 N reactions.