Synthetic, structural and inelastic neutron scattering studies of the hydrido-bridged cationic complexes [(PMe3)2(Y)Pt(μ-H)Pt(Y)(PMe3) 2]+ (Y = Ph, C6F5, C6Cl5) and of [(PEt3)2(H)Pt(μ-H)Pt(Ph) (PEt3)2]+

Alberto Albinati, Stanislav Chaloupka, Jürgen Eckert, Luigi M. Venanzi, Martin K. Wolfer

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Abstract

The mono-hydrido-bridged diplatinum complexes [(PMe3)2(C6X5)Pt(μ-H)Pt(C 6X5) (PMe3)2] (CF3SO3) (X = H, F, Cl) were prepared from the corresponding mononuclear species trans-[PtH(C6X5) (PMe3)2] and trans-[Pt(C6X5) (S) (PMe3)2] (CF3SO3) (S = weakly coordinating solvent). The X-ray crystal structures of [(PMe3)2(Ph)Pt(μ-H)Pt(Ph) (PMe3)2] [BPh4], prepared from the corresponding triflate (spacegroupP1̄, a = 13.731(5), b = 16.192(2), c = 23.425(8) Å, α = 96.46(2), β = 100.54(3), γ = 95.05(2)°, Z = 4, R = 0.043, Rw = 0.056 for 6914 observed reflections) and of [(PMe3)2(C6F5) Pt(μ-H)Pt(C6F5) (PMe3)2] (CF3SO3)·CH2Cl2 (space group P21/n, a = 11.762(2), b = 19.500(3), c = 19.112(3), β = 105.64(1), Z = 4, R = 0.038, Rw = 0.049 for 2528 observed reflections) were determined. Both cations contain the two planar [Pt(C6X5) (PMe3)2) moieties bridged by a hydride ligand, the Pt-Pt bonds being 3.0641(7) and 3.0969(9) Å for X = H and 3.009(1) Å for X = F. Inelastic incoherent neutron scattering studies were carried out on [(PMe3)2(C6F5)Pt(μ-H)-Pt(C 6F5)(PMe3)2] (CF3SO3), [(PEt3)2(H)Pt(μ-H)Pt(Ph)(PEt3) 2](CF3SO3) and [(PEt3)2(Ph)Pt(μ-H)Pt(Ph)(PEt3)2] (CF3SO3), and vibrational data for the Pt-H-Pt fragments obtained. The values of the Vasym/vsym ratios and a semi-empirical correlation were used to obtain approximate values of the Pt-H-Pt bond angles in compounds of this type.

Original languageEnglish
Pages (from-to)305-316
Number of pages12
JournalInorganica Chimica Acta
Volume259
Issue number1-2
DOIs
StatePublished - Jun 1997

Keywords

  • Crystal structures
  • Diplatinum complexes
  • Inelastic incoherent neutron scattering spectroscopy
  • Mono-hydrido-bridged compounds
  • Phosphine complexes

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