Within the field of metal-ligand cooperative base metal [TCM1] catalysis, mixed phosphine/amide donor ligands have proven to be particularly adept at bifunctional substrate activation across the metal–amide bond. Less attention, however, has been focused on possible functionality of the phosphine donors. In this work, we explore the metal-assisted oxidation of phosphine (+III) donors within a tetradentate bis(amido)bis(phosphine) iron(II) framework, (PNNP)Fe. The putative mechanisms of these transformations include reactive nascent Fe–E intermediates (with likely Fe=E multiple bond character) before insertion into the Fe–P bond to form Fe–E–P species (E = O, CR<sub>2</sub>, NR). Evidence forintermediates in the phosphine oxidation process arise from climbing image nudged elastic band (NEB-CI) transition state calculations as well as crystallographic characterization.

Phosphine oxidation assisted by a tetradentate bis(amido)bis(phosphine) iron(II) complex

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