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

Abstract

AbstractThe 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.