Hydride complexes of six-co-ordinate platinum

Abstract

Novel hydride complexes of six-co-ordinated platinum have been prepared in methylene chloride solution and studied by ¹H n.m.r. spectroscopy, double resonance experiments giving information about ³¹P and ¹⁹⁵Pt nuclei. HX adds to trans-[PtHY(PEt₃)₂](X,Y = Cl, Br, or I) to give cis-trans-[PtH₂XY(PEt₃)₂]. If X ≠ Y, halogen exchange occurs to give an approximately random mixture of dihydride products. Similarly HX adds to trans-[PtY₂(PEt₃)₂] to give PtHXY₂(PEt₃)₂, with H initially trans to X. Subsequent rearrangement gives the product with the lighter halogen trans to H. Addition of X₂ to trans-[PtHX(PEt₃)₂](X = Cl or Br) does not give the expected PtHX₃(PEt₃)₂, but a mixture of PtH₂X₂(PEt₃)₂ and PtX₄(PEt₃)₂. The complexes cis-cis-trans-[PtH₂X₂(PEt₃)₂](X = Cl or Br) were also characterised by C,H analysis and i.r. and Raman spectroscopy.