Shilov catalysis

Nucleophihc attack on a Pt(IV) alkyl has been proposed as the product forming step in Shilov catalysis wherein alkanes are converted to alcohols and alkyl chlorides using Pt salts in aqueous solution [40, 41, 53, 54]. Kinetic studies of the proposed product-forming step using the model platinum complex [MePtCls] found that the loss of a chloride ligand occurs prior to nucleophilic attack [40,41]. As these investigations were carried out in aqueous solution, it was not possible to... 

Dvorko and Shilov [Kinetics and Catalysis, 4 (212), 1964] have studied the iodine catalyzed addition of HI to cyclohexene in benzene solution. 

Shilov, A. E. Shul pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocations in the Presence of Metal Complexes. 2000. Catalysis by Metal Complexes, Volume 21. James,... 

Shilov devoted his review [12] to the development of selective and non-waste processes. He discusses the questions of organized molecular system (or ensembles) construction. Note that in the case of usual catalysis, catalytic sites freely interact with substrate molecules. This process is characterized by the absence of complementary activity. This is the reason for the relatively low selectivity of catalytic reactions. However, from positions of applied catalysis, such a catalytic system possesses clear advantages ... 

For reactions which usually involve enol or enolate intermediates, enamine formation has been postulated for primary and secondary amine catalysis in order to explain abnormally high catalytic effects and abnormal rate laws. Shilov, Yashinov and coworkers (for the last paper of the series, see Volkova... 

Dzhabiev, T.S., Mironova, S.A., and Shilov, A.E. (1999) Kinetic evidence of nitrogen reduction in the coordination sphere of a polynuclear complex, Kinetics and Catalysis (Translation of Kinetika i Kataliz) 40, 764-768. 

Likhtenshtein, G.I. (1986) On mechanisms of redox reactions with participation of metalloenzymes and their models, in Shilov, A. E. (eds.), Fundamental research in homogeneous catalysis, Gordon and Breach, New York, pp 325-334. 

Shilov, A.E.(1984) Dinitrogen fixation in model systems, in Mechanisms of Catalysis. Part II, Nauka, Novosibirsk, pp. 135-155,... 

Shilov et al studied the rate of oxidation of formate ions in phosphate and carbonate buffers, and showed that the reaction with molecular chlorine is negligible in solutions of pH > 6. At 20 °C the rate of reaction with hypochlorous acid is constant in the range pH 5.5-7, then it decreases with increase of pH, and becomes negligible at pH 13. The kinetics are second-order with respect to hypochlorous acid, and first with respect to formate ions. In alkaline solution hydroxide ion catalysis is apparent viz. 

One final report of alkane activation has been reported by Moiseev. The mechanism of the reaction was not investigated, but this system might be classified as an electrophilic activation of methane, either of the Shilov type or of the concerted four-center type (Fig. lc) where X=triflate. Reaction of methane with cobalt(III)triflate in triflic acid solution leads to the formation of methyltriflate in nearly stoichiometric quantities (90% based on Co) (Eq. 18). Carbon dioxide was also observed, but not quantified. Addition of 02 led to catalysis (four turnovers) [79]. 

AP Moravsky, AV Khramov and AE Shilov (1984) Fourth Intern Symp on Plomogeneous Catalysis. Abstract Book 4, pp 219-220. Sept 24-28. Leningrad... 

A. E. Shilov, in M. Gratzel, ed.. Energy Resources through Chemistry and Catalysis, Academic Press, 1983, p, 533. 

James, B.R. (1986). Transition metal catalyzed oxidations. In A.E. Shilov (ed.), Funda-mentals of Research in Homogeneous Catalysis. Gordon Breach, New York, pp. 309-324. 

The work of Farrell and Mason (1963) is related to Shilov and Weinstein s (1958) investigations on kinetic isotope effects in the iodination of dimethylaniline and other derivatives of aniline. There the unexplained fact exists that some iodinations are subject to general base catalysis but do not show an isotope effect (e.g. m-dimethyl-aminobenzenesulphonic-2,4,6-d3 acid), (Kurakin and Shilov, 1957 Weinstein and Shilov, 1958, 1960 Weinstein et al., 1960). 

A. Yamamoto, F. Ozawa, and T. Yamamoto, in Fundamental Research in Homogeneous Catalysis, A. E. Shilov, Ed., Gordon Breach Science Publishers, London, 1986, 181. 

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