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Pt(II) complexes in activation of saturated hydrocarbons
Authors:N F Gol'dshleger and A A Shteinman
Institution:(1) Division of the Institute of Chemical Physics, Chernogolovka, Moscow District, USSR
Abstract:The rate constants of deuterium exchange for cyclohexane in CH3COOD/D2O have been measured in the presence of 12 complexes of Pt(II) with various ligands (Cl, H2O, NH3, Br, NO2, py, DMSO, PPh3, etc.). The change in the rate constant is shown to follow the reverse series of the trans-effect of Pt(II) ligands. The rate constant of the interaction of PtCl2Sn (S is H2O, CH3COOH, n=1, 2) with cyclohexane in CH3COOD/D2O (1ratio1), k, equals 2.5×108 exp (–18200/RT) 1 mol–1 sec–1 (at 354–385 K). The ratio of rate constants for PtCl2S2, PtCl3S and PtCl 4 2– is 100ratio6ratio0.5 at 100°C.
Icyzcymcyiecyrcyiecyncyycy kcyocyncyscytcyacyncytcyycy scykcyocyrcyocyscytcyicy dcyiecyjcytcyiecyrcyocyocybcymcyiecyncyacy tscyicykcylcyocygcyiecykcyscyacyncyacy vcy scyrcyiecydcyiecy CH3COOD–D2O pcyrcyicy kcyacytcyacylcyicyzcyiecy 12-yucy kcyocymcypcylcyiecykcyscyacymcyicy Pt(II) scy rcyacyzcylcyicychcyncyycymcyicy lcyicygcyacyncydcyacymcyicy (Cl, H2O, NH3, Br, NO2, rcyucy, DMCO, PPh3 icy dcyrcy.). Pcyocykcyacyzcyacyncyocy, chcytcyocy icyzcymcyiecyncyiecyncyicyiecy kcyocyncyscytcyacyncytcyycy scykcyocyrcyocyscytcyicy scylcyiecydcyucyiecytcy ocybcyrcyacytcyncyocymcyucy rcyyacydcyucy tcyrcyacyncyscyecyfcyfcyiecykcytcyacy lcyicygcyacyncydcyocyvcy ucy Pt(II). Dcylcyyacy kcyocymcypcylcyiecykcyscyacy PtCl2Sn (S–H2O, CH3COOH, n=1,2) kcyocyncyscytcyacyncytcyacy scykcyocyrcyocyscytcyicy vcyzcyacyicymcyocydcyiecyjcyscytcyvcyicyyacy iecygcyocy scy tscyicykcylcyocygcyiecykcyscyacyncyocymcy vcy 1ratio1 CH3COOD–D2O k=2,5·108 exp(–18200/RT)lcy. mcyocylcysoftcy–1 scyiecykcy–1 (354–385°Kcy). Kcyocyncyscytcyacyncytcyycy scykcyocyrcyocyscytcyicy pcyrcyicy 100°C dcylcyyacy PtCl2S2, PtCl3S icy PtCl 4 2– ocytcyncyocyscyyacytcyscyyacy mcyiecyzhcydcyucy scyocybcyocyjcy kcyacykcy 100ratio6ratio0,5.
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