Effect of chalcogens on CO insertion into the palladium-methyl bond of [(N^N^X)Pd(CH3)](+) (X = O, S, Se) and on CO/ethylene copolymerisation.

Neutral chloromethylpalladium(II) complexes, [Pd(Cl)(CH3)(L)] (1a-5a) with ligands κ(2)-N^S-2-((3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl)-6-(phenylthiomethyl)pyridine (L1), κ(2)-N^S-2-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-(phenylthiomethyl)pyridine (L2), κ(2)-N^Se-2-((3,5-di-tert-butyl-1H-pyrazol-1-yl)methyl)-6-(phenylselanylmethyl)pyridine (L3), κ(2)-N^Se-2-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-(phenylselanylmethyl)pyridine (L4), and κ(2)-N^N-2-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-6-(phenoxymethyl)pyridine (L5) have been synthesised and characterised by various spectroscopic techniques. Ligands L1-L4 exhibit Npy^S/Se bidentate coordination whereas L5 shows an Npy^Npz bidentate coordination mode in their corresponding neutral palladium complexes. Abstraction of chloride in neutral palladium complexes with NaBAr4 (BAr4 = tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate) resulted in the formation of the cationic palladium complexes 1b-5b, in which L1-L4 adopt a tridentate Npz^Npy^X (X = S or Se) coordination mode in their respective cationic palladium complexes (1b-4b) whilst L5 in complex 5b adopts a Npy^Npz bidentate coordination mode and the palladium centre is stabilized by the weakly coordinating acetonitrile. Compounds 1b-5b readily undergo CO insertion into the Pd-CH3 bond to form Pd-acyl that determines their ability to catalyse CO/ethylene copolymerisation to polyketones.