Synthesis and Reactivity of Iron and Cobalt Bis(amidophosphine selenide) Complexes

We report the synthesis of two metal bis(amidophosphine selenide) complexes, ML2 (M = Fe, Co; L = SePPh2N(−)Tol), and investigate their reactivity toward ligand binding and oxidation with oxygen atom transfer reagents, pyridine-N-oxide and mesityl nitrile oxide. The oxidative strength of the reagent dictates the nature of the reactivity: either the ligand is oxidized, leading to the formation of a bimetallic mixed-ligand complex [MLL′]n, (L′ = OPPh2N(−)Tol), or the metal center is oxidized, resulting in a bimetallic μ-oxo complex [FeL2]2(μ2-O). This study defines a chemical space in which amidophosphine selenide ligands maintain their structural integrity.