The synthesis of an air-stable series of Pd 0 complexes with unsymmetric bidentate N-pyridine N-heterocyclic carbene ligands has been described. The carbenes were generated by synthesis of the silver(I) complexes from the imidazolium salts, followed by transmetallation of the C-N ligands to obtain the target electron-rich zerovalent palladium compounds. The bidentate coordination behaviour of the ligands was confirmed by 1 H, 13 C NMR and X-ray spectroscopy. The complexes are active precatalysts for the selective transfer semihydrogenation of alkynes to Z-alkenes, with selectivities up to 99%.
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