Abstract
The reaction of the Pt(II) dihydride complex cis-[PtH2(dcype)](dcype = 1,2-bis(dicyclohexylphosphino)ethane) with the primary or secondary phosphine-borane adducts PhRPH x BH3(R = H, Ph) was found to exclusively afford the mono-substituted complexes cis-[PtH(PPhR x BH3)(dcype)](1: R = H; 2: R = Ph)via a dehydrocoupling reaction between Pt-H and P-H bonds. Similar reactivity was observed between the uncoordinated phosphines PhRPH (R = H, Ph) and cis-[PtH2(dcype)], which gave cis-[PtH(PPhR)(dcype)](4: R = H; 5: R = Ph). The complexes were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, IR, MS and, in the case of 2, X-ray crystallography that confirmed the cis geometries. The di-substituted complex cis-[Pt(PhPH x BH3)2(dcype)](3) was prepared from the reaction of cis-[PtCl2(dcype)] with two equivalents of Li[PPhH x BH3]. This suggested that steric reasons alone cannot be used to explain the lack of reactivity with respect to a second dehydrocoupling reaction involving the remaining Pt-H bond in complexes 1, 2, 4 and 5.
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