PALLADIUM AND PLATINUM COMPLEXES OF α-KETOESTERS. CRYSTAL STRUCTURE OF

Article abstract of DOI:10.1016/0022-328X(85)87421-0

The reactions of M(PCy3)2 (3) (a, M=Pd; b, M=Pt; Cy=cyclohexyl) and trans-PtH2(PCy3)2 (4) with the α-ketoesters diethyloxomalonate (1) and ethylpyruvate (2) have been investigated.At room temperature 1 coordinates strongly to 3, whereas 2 yields labile adducts.At higher temperatures 2 reacts with 3b to yield the enolate (8), the structure of which has been determined by X-ray diffraction.The ester 1 behaves like CO2 in undergoing rapid insertion into the Pt-H bond of 4.Unexpectedly reaction of 2 with 1 does not yield an insertion product, but again gives complex 8.