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

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. (Abstract present only on the URL page and not on the pdf version)