Metal-ligand cooperativity has emerged as a viable strategy for promoting s-bond activation. The ligand can participate in two potential ways, ligand-based redox activity or by direct ligand involvement in the s-bond cleavage events, which eliminates the redox requirements of the metal center. N-heterocyclic phosphenium/phosphido ligands (NHP) with chelating diphosphine sidearms can enforce coordination to metal centers while imparting stability on the resulting complex. When incorporated in the tridentate framework (PPP) the NHP+can be reduced to the anionic NHP-form, which can allow for ligand-based redox processes. The metal-ligand cooperativity of the cobalt NHP complexes is explored through exploration of the rich redox profiles of the monomers and dimers and through the activation of various E-H bonds (E = H, O, S, B) across the metal-PNHP bond. The goal is to develop catalytic methods that incorporate metal-ligand cooperativity using NHP ligands.

Synthesis and reactivity of cobalt N-heterocyclic phosphenium/phosphido complexes

2019 Fall National Meeting

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