A Snapshot of P4 Tetrahedron Opening: Rh‐ and Ir‐Mediated Activation of White Phosphorus

Abstract

P's in a pod: White phosphorus reacts with [M(dppm)2]OTf (M=Rh, Ir; dppm=PPh2CH2PPh2) to give [M(dppm)(Ph2PCH2PPh2PPPP)]OTf whereby a trihapto “P5” ligand is assembled through PP bond formation between one dppm PPh2 group and an activated P4 molecule (see scheme; P green, M red, C white, phenyl groups omitted). A bimetallic reaction pathway leading to the final product is proposed, as based on in situ 31P NMR studies.