Transfer of cyclopentadienyl groups between platinum atoms

Abstract
Replacement of a chloride ion of cis-[PtCl2(CO)(PR3)](PR3= tertiary phosphine) by a cyclopentadienyl group from Tl(C5H5) or Hg(C5H5)2 results exclusively in the isomers of [PtCl(σ-C5H5)(CO)(PR3)] with C5H5trans to PR3. The second chloride can be replaced when excess Tl(C5H5) is used. The σ-bonded cyclopentadienyl groups of either mono- or di-substituted compounds can readily exchange in solution with a chloride of cis-[PtCl2(CO)(PR3)] again producing exclusively the same isomers of [PtCl(σ-C5H5)(CO)(PR3)]. The cyclopentadienyl groups do not transfer as fast as chloride ions between the same species, but do so considerably faster than any accompanying CO scrambling processes. Cyclopentadienyl groups from the σ-bonded complexes, and from [Pt(η5-C5H5)(PR3)2]Cl, can also be readily transferred to mercury when treated with HgCl2.

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