Abstract
The hexafluorobut-2-yne complexes, Pt(CF3CCCF3)L2(L = PPh3, PMePh2, PMe2Ph, PEt2Ph; 2L = Ph2PCH2CH2PPh2) react with trifluoroacetic acid to give the square planar alkenyl complexes, Pt(OCOCF3)(CF3CCHCF3)L2 in which the phosphine ligands have a relative cis-configuration. The complex, cis-Pt(OCOCF3)(CF3CCHCF3)(PPh3)2 can be thermally isomerised to its trans-isomer and cis–trans isomerisation also occurs in [2H6] acetone solution. The action of heat on cis-PtCl(CF3CCHCF3)(PMePh2)2 also effects isomerisation to the trans-isomer. Mercury(II) chloride and bromide similarly react with Pt(CF3CCCF3)(PPh3)2 and Pt(CF3CCCF3)(PMePh2)2 to give the mercuriated products [PtCl{CCF3C(HgCl)CF3}(PPh3)2] and cis-[PtX{CF3CC(HgX)CF3}(PMePh2)2](X = Cl or Br). Protonation of RhCl(CF3CCCF3)(PPh3)2 and IrCl(CO)(CF3CCCF3)(PPh3)2 gives the alkenyl complexes RhCl2(CF3CCHCF3)(PPh3)2 and IrCl(OCOCF3)(CF3CCHCF3)(CO)(PPh3)2 respectively but W(MeCN)(CF3CCCF3)3 does not react with trifluoroacetic acid under normal conditions.
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