The coupling of bridging diphenylphosphanides (PPh₂^-) with terminally bonded anionic ligands (L^-) that takes place onto polynuclear Pt or Pd systems is reviewed. The two-electron reduction that accompanies the PPh₂/L coupling generally implicates a M(IV) centre but there are examples where the redox process involves a M(II),M(II) system that is transformed into a M(I),M(I) containing product (M = Pd, Pt). The discussed coupling reactions end up with formation of new ligands which, depending on the nature of L^-, display P-E bonds with E = C, N, O, P, S and I.