The formation and cleavage of chemical bonds in catalytic reactions relies on accessible two-electron redox processes that are often challenging for base metals such as first row transition metals. At the heart of this challenge is deliberate and systematic ligand design to tune the reactivity at transition metal centers by manipulating their electronic structure. Moreover, metal-ligand cooperativity is a strategy that can enabe heterolytic bond cleavage processes and/or facilitate redox processes. A tetradentate bis(amido)bis(phosphine) ligand has been coordinated to iron(II) and it has been shown that the resulting complex, (PNNP)Fe, can activate two B-H σ bonds across the two iron-amide bonds in the molecule in an overall four-electron process that does not require a change in the metal formal oxidation state. This ligand-enabled pathway allows for novel reactivity at first-row metals that warrant continuing investigation. The activation of Si–H bonds and formation of Si–Si bonds across Fe–amide bonds in (PNNP)Fe will be discussed, along with progress towards additional metal-ligand cooperative reactions and extension to (PNNP)Co systems.

Activation of element-hydrogen bonds across metal-amide bonds in first row transition metal bis(amido)bis(phosphine) complexes, (PNNP)M

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