Synthetic, structural and inelastic neutron scattering studies of the hydridobridged cationic complexes [(PMe 3) 2(Y) Pt(μ-H)Pt(Y)(PMe 3) 2] + (Y = Ph, C 6F 5, C 6Cl 5) and of [(PEt 3) 2(H)Pt(μ-H) Pt(Ph) (PEt 3) 2]

• Published in: Inorganica Chimica Acta 1997-06, Vol.259 (1), p.305-316
• Main Authors: Albinati, Alberto, Chaloupka, Stanislav, Eckert, Jürgen, Venanzi, Luigi M., Wolfer, Martin K.
• Format: Article
• Language: English
• Subjects: Crystal structures; Diplatinum complexes; Inelastic incoherent neuuoa scandag spectroscopy; Mono-hydrido-bridged compounds; Plwsphine complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(97)05509-6

The mono-hydrido-bridgeddiplatinumcomplexes [(PMe 3) 2(C 6X 5)Pt(μ-H)Pt(C 6X 5)(PMe 3) 2](CF 3SO 3) (X = H, F, Cl) were prepared from the corresponding mononuclear species trans- [PtH(C 6X 5)(PMe 3) 2] and trans-[Pt(C 6X 5)(S)(PMe 3) 2](CF 3SO 3) (S-weakly coadinating solvent). The X-ray crystal structures of [(PMe 3) 2(Ph)Pt(μ-H)Pt(Ph)(PMe 3) 2] [BPh 4], prepared from the cares triflate (space group P 1, a=13.731(5), b=16.192(2), c=23.425(8) A ̊ , α=96.46(2), β=100.54(3), y=95.05(2)°, Z=4, R=0.043, R w =0.056 for 6914 observed reflections) and of [(PMe 3) 2(C 6F 5)Pt(μ-H)Pt(C 6F 5)(PMe 3) 2](CF 3SO 3)-CH 2Cl 2 (space group P2 1/ n, a=11.762(2), b=19.500(3), c=19.112(3), β=105.64(1), Z=4, R=0.038, R W=0.049 for 2528 observed reflections) were determined. Both cations contain the two planar (Pt(C 6X 5) (PMe 3) 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 [(PMe 3) 2(C 6)F 5)Pt(μ-H)-Pt(C 6F 5)(PMe 3) 2](CF 3SO 3), ( PEt 3) 2( H) Pt( μ- H) Pt( Ph)( PEt 3) 2]( CF 3 SO 3) and [( PEt 3) 2( Ph) Pt( μ- H) Pt( Ph)( PEt 3) 2]( CF 3 SO 3), and vibrational data for the PtHPt fragments obtained. The values of the ν asynm/ ν sym ratios and a semi-empirical correlation were used to obtain approximate values of the Pt-H-Pt bond angles in compounds of this type.