Reactivity of a Strictly T-Shaped Phosphine Ligated by an Acridane Derived NNN Pincer Ligand

Abstract

The steric tuning of a tridentate acridane-derived NNN pincer ligand allows for the isolation of a strictly T-shaped phosphine that exhibits ambiphilic reactivity. Well-defined phosphorus-centered reactivity towards nucleophiles and electrophiles is reported, contrasting with prior reports on this class of compounds. Reactions towards oxidants are also described. The latter result in the two-electron oxidation of the phosphorus atom from +III to +V and are accompanied by a strong geometric distortion of the NNN pincer ligand. By contrast, cooperative activation of E−H (HCl, HBcat, HOMe) bonds proceeds with retention of the phosphorus redox state. When using H2O as a substrate, the reaction results in the full disassembly of H2O to its constituent atoms, highlighting the potential of this platform for small molecule activation reactions.