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- W1963796543 abstract "Abstract Homogeneous solutions of several tertiary phosphine complexes of Ir, Pt, Ru, and Rh have been tested for their catalytic activity for (1) para-hydrogen conversion, p − H2 ⇄ o − H2, and (2) hydrogen-deuterium equilibration, H2 + D2 → 2 HD. The experiments were carried out in toluene under 1 atm of hydrogen and between 25 and 65°C. The following results were obtained. (1) para-H2 conversion: (a) active complexes: trans-[Ir(A)(CO)(Ph3P)2] (A = Cl, Br, or I), [Pt(Ph3P)4], {Pt(Ph3P)n}, [Pt(O2)(Ph3P)2], [Pt(Cl)2(Bu3P)2], and [Ru(Cl)2(Ph3P)3]; (b) inactive complexes: [Pt(PC2P)2], [Pt(PCCP)2], and [Fe(DPGH)2(py)2]. (2) H2-D2 equilibration: (a) active complexes: trans-[Ir(A)(CO)(Ph3P)2], {Pt(Ph3P)n}, and [Pt(O2)(Ph3P)2]; (b) inactive complexes [Pt(Ph3P)4], [Pt(Cl)2(Bu3P)2], and trans-[Rh(Cl)(CO)(Ph3P)2]. The H2-D2 catalysis by the iridium complexes was accompanied by an exchange between D2 and some bound hydrogens in the reaction system. It is proposed that the para-H2 conversion proceeds via a chemical mechanism through a dihydrido intermediate M(H)2. The H2-D2 equilibration is tentatively proposed to involve a tetra-(hydrido-deuterio) species, M(H, D)4, representing a labile intermediate or an activated complex. Alternate mechanisms for the H2-D2 equilibrium are considered, and their relative merits are discussed." @default.
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- W1963796543 date "1982-02-01" @default.
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- W1963796543 title "para-Hydrogen conversion and hydrogen-deuterium equilibration catalyzed by diamagnetic iridium, platinum, and ruthenium complexes in nonaqueous solution (1)" @default.
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- W1963796543 doi "https://doi.org/10.1016/0021-9797(82)90006-6" @default.
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