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1.
S. A. Mitchenko V. P. Ananikov V. V. Zamashchikov 《Theoretical and Experimental Chemistry》1996,32(4):205-208
Propargyl alcohol in aqueous Pt(IV) iodide solutions at 10–15°C gives the product of the addition of PtIV and iodide to the triple bond, isolated as PtIV(CH=Cl-CH2OH)2I2(CH3OH). The vinyl ligands in this complex are in cis position. The complex decomposes at 80°C to give E,E-2,5-diiodo-2,4-hexadiene-1,6-diol and PtI2. The E, E structure of the diene indicates trans addition of PtIV and I– to the alkyne in the iodoplatination steps.L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg St., 340114 Donetsk, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 4, pp. 234–237, July–August, 1996. Original article submitted October 17, 1995. 相似文献
2.
R. S. Mitchenko A. A. Shubin T. V. Krasnyakova 《Theoretical and Experimental Chemistry》2006,42(5):314-319
A heterogeneous catalyst for the hydrochlorination of acetylene by gaseous HCl is formed as a result of mechanical treatment
of the solid salt K2PtCl4 in an atmosphere of acetylene, ethylene, or propylene by the formation of π complexes of platinum(II) as active centers in
the surface layer under these conditions. The controlling stage of the catalytic reaction is chloroplatination of the π-coordinated
acetylene by the HCl molecule. The reaction takes place as a concerted process, in which an intermediate β-chlorovinyl derivative
of platinum(II), a complex of platinum with a coordination vacancy[PtCl
3
*
]−, and a new molecule of HCl are formed simultaneously with cleavage of the H—Cl and Pt—Cl bonds in the metal complex adjacent
to the π-acetylene complex. The catalytic cycle closes with rapid dissociation of the organoplatinum intermediate by the action
of HCl, giving the final product and the initial complex [PtCl4]2−.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 306–311, September–October, 2006. 相似文献
3.
Mitchenko S. A. Khomutov E. V. Zhikharev I. V. Beletskaya I. P. 《Kinetics and Catalysis》2002,43(4):475-483
Mechanical treatment of the K2PtCl4 solid salt in a vibrating mill results in Pt–Cl bond heterolysis to form coordinatively unsaturated Pt(II) complexes. At room temperature, the freshly treated K2PtCl4 salt absorbs methyl bromide and evolves methyl chloride to the gas phase. The reaction mechanism involves the following sequence of steps: the oxidative addition of methyl iodide to Pt(II) with the intermediate formation of Pt(IV) methyl complexes and the decomposition of the latter due to intramolecular reductive elimination with methyl chloride formation. The first step of the reaction of MeI with the preactivated surface of the K2PtCl4 salt is assisted by active sites, which are regenerated in each act of the chemical transformation of MeI into MeCl involving in the chain substitution of halogen in methyl iodide. The coordinatively unsaturated surface platinum complexes can act as such active sites. Due to their effective positive charge, they can provide electrophilic assistance to nucleophilic substitution. Chain termination is probably due to the coordination of the complex with a coordination vacancy and an interstitial chloride ion to the inactive K2PtCl4 complex. 相似文献
4.
5.
Zubkov I. N. Soromotin V. N. Savost’yanov A. P. Mitchenko S. A. Yakovenko R. E. 《Kinetics and Catalysis》2022,63(2):218-225
Kinetics and Catalysis - The results of a study of the synthesis of products from CO and H2 on a supported industrial Co–Al2O3/SiO2 catalyst under medium and high pressures in the gas... 相似文献
6.
7.
Ananikov V. P. Mitchenko S. A. Beletskaya I. P. 《Russian Journal of Organic Chemistry》2002,38(5):636-650
Activation of the CÍÄC bond in acetylenic hydrocarbons, catalyzed by iodide complexes of platinum(IV), and the subsequent CÄC coupling reaction make it possible to synthesize 1,4-diiodo-substituted dienes with high stereo- and regioselectivity. The reaction involves intermediate formation of bis--vinyl platinum(IV) complexes which can be isolated in the pure state. Under similar conditions palladium(II) complexes catalyze iodine addition to acetylene. 相似文献
8.
T. V. Krasnyakova D. V. Nikitenko E. V. Khomutova S. A. Mitchenko 《Kinetics and Catalysis》2017,58(5):533-540
Two routes of catalytic hydrochlorination of acetylene were found by the isotopic label method for systems with supported palladium K2PdCl4/C and Н2PdCl4/C catalysts: with formation of the products of syn- and anti-addition of the H(D)Cl molecule to the triple bond of acetylene. Two isotopic effects that differ in magnitude were determined for these systems from the reaction kinetics and the ratio of the yields of the nondeuterated and monodeuterated isotopomers of the product, which are due to the participation of the H(D)Cl molecule in the two reaction stages: limiting chloropalladation and rapid protodemetallation. The effective activation energies and kinetic isotope effects coincided within the experimental errors, which suggests that the reaction mechanisms are similar and the active centers of the catalysts in systems with K2PdCl4/C and Н2PdCl4/C are of the same nature. 相似文献
9.
10.
Mitchenko S. A. Khomutov E. V. Kovalenko V. V. Beletskaya I. P. 《Kinetics and Catalysis》2002,43(4):469-474
Mechanochemical treatment of solid-phase K2PtX6 salts in a vibrating mill in an argon or air atmosphere produced paramagnetic Pt(III) complexes via the homolytic cleavage of the Pt–X bond. Lewis acid sites were found on the surface of the mechanically activated K2PtCl6 salt using the paramagnetic probe method. The sites can be attributed to coordinatively unsaturated Pt(IV) complexes formed via Pt–Cl bond heterolysis. 相似文献