78064-41-2Relevant academic research and scientific papers
reversible displacement of diydrogen by carbon monoxide in binuclear platinum complexes. Characterization of binuclear carbonyl complexes of platinum(1)
Fisher, John R.,Millis, Allan J.,Sumner, Steven,Brown, Michael P.,Thomson, Mary A.,Puddephatt, Richard J.,Frew, Alleen A.,Manojlovic-Mulr, Ljublca,Muir, Kennet W.
, p. 1421 - 1429 (2008/10/08)
The complex ion [Pt2H2(μ-H)(μ-dppm)2] (I), dppm = Ph2PCH2PPh2, reacts reversibly with carbon monoxide to give dihydrogen and a new hydridodiplatinum(Γ) complex cation, [P2H(CO)(μdppm)2]+ (II), which is structurally characterired by its IR and 1H and a1P|1H| NMR spectra. II reacts with PMe2Ph to give [Pt2H(PMe2Ph)(μ-dppm)2]+ and CO and with MeSH to give [Pt2H2(μ-SMe)(μ-dppm)2 and CO I is formed by reaction of [Pt2(CO)2(μ-dppm)2]2+ with excess H2. and reaction of [Pt2H2(μ-Cl)(μ-ppm)2]+ with CO gives [Pt2Cl(CO)(μ-dppm)2]+ thus eatablishing the generality of H2 for CO diaplacement reactions in diplatinum complexes. Complex I acts as a homogenous tatalygl for the water BUS shift reaction at 100°C in aqueous methinol, and model react urns indicate that a mechanism involving nome of the binuclear intermtdiates and reactions described above is reasonable The crystal structure of [Pt2(CO)2(μ-dppm)2][PF6] 2 was drteiminedby the heavy-atom method and relmed by full-matrix least iquares to P = 0.061 and Rw = 0.079, using 552b diffractometric X-ray inttnsitiefl with I > 3σ(I) Crystals are monocliruc of space group P21/c with a = 17.298 (5) A?, b = 18.913 (7) A?, c = 18.804 (4) A?, S = 98.63 a?, βid = 4. The structure of the cation contains two Pt-CO fragments bridgsd by two dppm ligands and kinked directly by a Pt-Pt σ bond of 2.623 (1) A?. The raetal-lisand hood lenjfthc are Pt-C = 1.92 (2) and 1.95 (2) A? and Pt-P = 2.302 (4)-2 340 (1) A?. Variations in The Pt-P distances are likely to arise from steric effects.
Binuclear reductive elimination reactions in diplatinum complexes: Synthesis of hydridoplatinum(I) complexes
Brown, Michael P.,Fisher, John R.,Hill, Ross H.,Puddephatt, Richard J.,Seddon, Kenneth R.
, p. 3516 - 3521 (2008/10/08)
The complex [Pt2H2(μ-H)(μ-dppm)2][PF6] (1) (dppm = Ph2PCH2PPh2) reacts with tertiary phosphine ligands to give H2 and the hydridoplatinum(I) complexes [Pt2HL(μ-dppm)2][PF6] (4, L = η1-dppm; 5, L = PMe2Ph; 6, L = PMePh2; 7, L = PPh3). Complex 4 is also obtained by the reduction of [Pt(dppm)2][PF6]2 with sodium borohydride. Study of the 1H and 31P NMR spectra of 4-7 is in accord with the presence of Pt-Pt bonds and, in the case of 4, shows that its structure in solution is similar to that previously determined in the solid state by an X-ray investigation. Methanethiol reacts reversibly with 4 to give [Pt2H2(μ-SMe)(μ-dppm)2][PF6]. Attempts to prepare diplatinum(0) complexes by deprotonation of 4 or 7 were unsuccessful.
