Dinuclear PCP pincer complexes from Lewis acidic [Pd(OTf)(PCP)] and basic [Pd(4-Spy)(PCP)] (OTf = triflate; 4-Spy = 4-pyridinethiolate; PCP = (-)CH(CH(2)CH(2)PPh(2))(2))

The Lewis acidic pincer with a labile triflate ligand, viz. [Pd(OTf)(PCP)] (PCP = (-)CH(CH(2)CH(2)PPh(2))(2)) was prepared from [PdCl(PCP)] with AgOTf. It reacts readily with neutral bidentate ligands [L = 4,4'-bipyridine (4,4'-bpy) and 1,1'-bis(diphenylphosphino)ferrocene (dppf)] to give dinuclear PCP pincers [{Pd(PCP)}(2)(micro-L)][OTf](2) (L = 4,4'-bpy, 2; dppf,3). [PdCl(PCP)] also reacts with 4-mercaptopyridine in the presence of KOH to give a Lewis basic pincer with a free pyridine functional group [Pd(4-Spy)(PCP)]4. Its metalloligand character is exemplified by the isolation of an asymmetric dinuclear double-pincer complex [{Pd(PCP)}(2)(micro-4-Spy)][PF(6)] 6 bridged by an ambidentate pyridinethiolato ligand. Complexes 1, 2, 3, 4 and 6 have been characterized by single-crystal X-ray diffraction analyses.