Probing the Structure,Dynamics, and Bonding of Coinage Metal Complexes of White Phosphorus

A series of cationic white phosphorus complexes of the coinage metals Au and Cu have been synthesised and characterised both in the solid state and in solution. All complexes feature a P₄ unit coordinated through an edge P?P vector (η²‐like), although the degree of activation (as measured by the coordinated P?P bond length) is greater in the gold species. All of the cations are fluxional on the NMR timescale at room temperature, but in the case of the gold systems fluxionality is frozen out at ?90 °C. Electronic structure calculations suggest that this fluxionality proceeds via an η¹‐coordinated M?P₄ intermediate.