Activation and Catalytic Reactions of Saturated Hydrocarbons by A.E. Shilov, Georgiy B. Shul'pin, Alexander E. Shilov
By A.E. Shilov, Georgiy B. Shul'pin, Alexander E. Shilov
This monograph is dedicated to the activation and numerous differences of saturated hydrocarbons (alkanes), i.e. reactions followed through the C--H and C--C bond cleavage. Alkanes are the most parts of oil and common fuel, and for that reason are the critical feedstocks for the chemical undefined. nevertheless, those elements are recognized to be the least reactive natural compounds. specified recognition is paid to the lately came upon alkane activations in the presence of steel complexes, that are defined in additional element. as well as the reactions of saturated hydrocarbons that are the major subject of this e-book, the activation of C--H bonds in arenes or even olefins and acetylenes are thought of. The monograph may be priceless not just should you have an interest in the activation of alkanes and different hydrocarbons via steel complexes, but in addition for experts in homogeneous and heterogeneous catalysis, petrochemistry, and organometallic chemistry. a few elements of the monograph might be of curiosity for experts in inorganic and natural chemistry, theoretical chemistry, biochemistry or even biology, and additionally in case you paintings within the petrochemical undefined, business natural synthesis and biotechnology.
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Additional resources for Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes
It was shown in the 1970s that alkanes are oxidized by platinum(IV) [11a], palladium(II) [11b], ruthenium(IV) [11c], and cobalt(III) [11d,e] compounds, and that complexes of iridium(III) [11f] and titanium(II) [11g] catalyze the H–D exchange. The next decade was marked by a vigorous development of studies on the activation of alkanes and arenes by low-valent metal complexes via an oxidative addition mechanism with the formation of alkyl and aryl derivatives of metals (or alkenes) . The number of known examples of the activation of the C–H bond by complexes of metals in a high oxidation state with formation of organometallic compounds is so far much less.
Investigation of the singlet state oxygen reaction with alkanes in the gas phase has revealed that two distinct channels exist for these reactions. They were interpreted as insertion into C–H bond and H atom abstraction. The insertion component dominates for small molecules with strong C–H bonds, while the abstraction component is the dominant mechanism for formation of OH radical in the cases of larger molecules with stronger steric hindrances and weaker C–H bonds. An insertion mechanism of the interaction of singlet state oxygen with methane was confirmed in ab initio theoretical calculations [8e].
A. Zh. Fiz. Khim. 1969, 43, 2174 (in Russian). 11. (a) Gol’dshleger, N. ; Es’kova, V. ; Shilov, A. ; Shteinman, A. A. Zh. Fiz. Khim. 1972, 46, 1353 (in Russian). (b) Rudakov, E. ; Zamashchikov, V. ; Belyaeva, N. ; Rudakova, R. I. Zh. Fiz. Khim. 1973, 47, 2732 (in Russian). (c) Tret’akov, V. ; Arzamaskova, L. ; Ermakov, Yu. I. Kinet. Katal. 1974, 15, 538 (in Russian), (d) Cooper, T. ; Waters, W. A. J. Chem. Soc. B 1967, 687. ; De Radzitsky, P. J. Chem. , Perkin Trans. 2. 1972, 2247. (f) Garnett, J.