Synthetic and reactivity studies of some asymmetric dinuclear platinum(II) monohydrido-bridged cations. The neutron diffraction structure of [(Pet3)2(Ph)Pt(μ-H)PtH(PEt3)2][BPh4]

• Published in: Inorganica Chimica Acta Vol. 265; no. 1-2; pp. 255 - 265
• Main Authors: Albinati, Alberto, Bracher, Gustav, Carmona, Daniel, Jans, Josef H.P., Klooster, Wim T., Koetzle, Thomas F., Macchioni, Alceo, Ricci, John S., Thouvenot, René, Venanzi, Luigi M.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.11.1997
• Subjects: Dinuclear complexes; Hydro-bridged complexes; Neutron diffraction; Platinum complexes; Hydro-bridged complexes; Neutron diffraction; Dinuclear complexes; Platinum complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(97)05746-0

The complexes [(PEt3)2(Ar)Pt(μ-H)PtH(PEt3)2][BPh4] (Ar=Ph,2,4-Me2C6H3, 2,4,6-Me3C6H22) were prepared and characterized. Multinuclear, multidimensional NMR studies of these complexes show that, in solution, (i) they exist in rapidly intercoverting conformers which retainn the bent Pt(μ-H)PtH moieties found in the solid state, (ii) the coordination at each platinum atom is square planar, (iii) the two coordination planes are perpendicular to each other and (iv) the aryl group is perpendicular to the coordination plane of the platinum atom to which it is bonded. The complex [PEt3)2Pt(μ-H)PtH(PEt3)2][BPh4] does not react with C2H4 and CH2:CH·CO2Me. At −60°C or above, [(PEt3)2(Ph)Pt(μ-H)PtH(PEt3)2)][BPh4] reacts with CO giving the platinum(II) cations trans-[PtX(CO)(PEt3)2](Ph)∗ (X=H and Ph), and [PtH(PEt3)3]+ and the platinum(0) carbonyl cluster [Pt4(μ-CO)3)4]. The cluster structure of I(PEt3)2(Ph)·Pt(μ-H)PtH(PEt3)2][BPh4, obtained by neutron diffraction, shows that the Pt-H-Pt bond angle in this cation is 125(1)° indicating that the interaction between these three atoms is weak.