In recent decades, interest in replacing noble metals with more sustainable first-row metals has been growing steadily. The primary disadvantage of first row metals in catalysis, however, is their decreased ability to undergo metal-centered two-electron processes—facile reactions for their heavier congeners. To combat this decreased reactivity, a non-innocent ligand can be employed to alleviate the redox burden via metal-ligand (M–L) cooperativity. In such a process, bonds in substrate molecules are heterolytically cleaved across the M–L bond without a concomitant change in oxidation state of the metal. This ligand-enabled pathway allows for novel reactivity at first-row metals that warrant continuing investigation. In this work, we explore the activation of small molecules across Fe–amide bonds in a tetradentate bis(amido)bis(phosphine) iron(II) complex (PNNPFe) and its derivatives.

Small molecule activation across Fe–amide bonds in a tetradentate bis(amido)bis(phosphine) iron(II) complex

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