Study of the interaction of platinum hydride complex + with carbon monoxide and ethylene in trifluoroacetic acid solutions

Article abstract of DOI:10.1016/0022-328X(89)87192-X

The most probable intermediate formed by interaction of CO and C2H4 with <(PPh3)3PtH>⁺ (I), in the synthesis of diethylketone from C2H4, CO and H2 under action of the catalytic system (PPh3)2Pt(OAc)2/PPh3/CF3COOH has been studied by 1H, 13C, 31P NMR spectroscopy.Complex I readily reacts with CO in CF3COOH solutions to form a carbonyl hydride complex trans-<(PPh3)2Pt(CO)H>⁺ (II).In contrast to I, II undergoes ethylene insertion at the Pt-H bond in the presence of a catalytic additive Sn(OAc)2.The carbonyl ethyl complex trans<(PPh3)2Pt(CO)(C2H5)>⁺ (III) formed quantitatively from this insertion is stable to isomerization to the corresponding complex indicating that the carbonylation of the Pt-ethyl bond is the rate-determining step of the diethyl ketone synthesis.