676-55-1Relevant articles and documents
Leight, J. R. C.,Zeiss, H. H.
, p. 391 - 393 (1970)
Catalytic Activation of Unstrained, Nonactivated Ketones Mediated by Platinum(II): Multiple C-C Bond Cleavage and CO Extrusion
Sarju, Julia P.,Dey, Debashish,Torroba, Javier,Whitwood, Adrian C.,Redeker, Kelly,Bruce, Duncan W.
supporting information, p. 4539 - 4542 (2019/11/29)
The complexes [Pt(tolpy)Cl(L)] (tolpy = 2-(4-tolyl)pyridyl; L = dmso, dms, py, PPh3, CO) are precursors for the catalytic cleavage of C-C bonds and extrusion of CO from a series of unactivated ketones such as cyclohexanone; deuterium labeling experiments demonstrate the involvement of a transfer hydrogen step in the mechanism.
High-temperature Shilov-type methane conversion reaction: Mechanistic and kinetic studies
Kang, Shujuan,Ma, Qisheng,Chen, Weiqun,Chen, Guanyi,Tang, Yongchun
, p. 1777 - 1784 (2015/10/20)
Traditional Shilov reactions (performed in aqueous solution with a PtCl2 catalyst) for methane conversion suffer from catalyst deactivation at high temperatures (> 100 °C), therefore only very low conversion rates have been achieved. In this paper, we show that Shilov-type C-H activations are achievable at much higher temperatures (～200 °C) by addition of concentrated aqueous solutions of Cl- to inhibit Pt catalyst precipitation. Various chloride-based ionic liquids also stabilized the Pt catalyst at mild reaction temperatures (～140 °C). Under high-pressure conditions (> 25.5 MPa), achieved using a specially designed sealed gold-tube reactor, very high methane conversion rates (> 90%) were obtained; this is attributed to the improved methane solubility in aqueous solution. Deuterium isotope (H/D) exchange between methane and water was used to examine the reaction reactivity and selectivity. Multiply D-substituted products were observed, indicating that multiple C-H activations occurred. A comprehensive network reaction that included all the chain reactions was set up to clarify the reactivities and product selectivities of the methane activation reactions. The reaction network consisted of a series of parallel first-order reactions, which can be described by the Arrhenius equation. The kinetic parameters such as the frequency factor, activation energies, and stoichiometric coefficients were obtained by fitting the experimental data. Because all four C-H bonds in a methane molecule are equivalent, multiple substitutions during methane conversion cannot be avoided. Our studies indicate that mono-substituted and di-substituted methane isotopologue generations have similar activation energies, suggesting that the highest mono-substitution selectivity cannot be greater than 50%.
