Structural characterisation of solution species implicated in the palladium-catalysed Heck reaction by PdK-edge X-ray absorption spectroscopy: palladium acetate as a catalyst precursor

Energy dispersive EXAFS (EDE), Quick EXAFS (QEXAFS), C-13 NMR and X-ray crystallography have been used to probe the co-ordination sphere of palladium in the course of the phosphine free Heck reaction. [Pd2I6][NBu3H](2) has been isolated from the precatalytic solution and its crystal structure determined. EDE and QEXAFS spectra of the complexes Pd(OAc)(2), Pd(PPh3)(4) and [Pd2I6][NEt3H](2) illustrated the value of the technique in structure elucidation. EXAFS of the precatalytic solution detects [Pd2I6](2-) and no co-ordinated carbon. EXAFS of the catalytic solution shows a first co-ordination sphere of 2 carbon atoms and a second of 2-2.5 iodines. A scheme involving an equilibrium between the oxidative addition product and the olefin co-ordination species, has been proposed to explain these results.