By A.E. Shilov, Georgiy B. Shul'pin, Alexander E. Shilov
ISBN-10: 0792361016
ISBN-13: 9780792361015
This monograph is dedicated to the activation and diverse changes of saturated hydrocarbons (alkanes), i.e. reactions followed by means of the C--H and C--C bond cleavage. Alkanes are the most ingredients of oil and traditional fuel, and hence are the critical feedstocks for the chemical undefined. nonetheless, those elements are recognized to be the least reactive natural compounds. unique consciousness is paid to the lately discovered alkane activations in the presence of steel complexes, that are defined in additional aspect. as well as the reactions of saturated hydrocarbons that are the major subject of this publication, the activation of C--H bonds in arenes or even olefins and acetylenes are thought of. The monograph should be invaluable not just in the event you have an interest in the activation of alkanes and different hydrocarbons by means of steel complexes, but in addition for experts in homogeneous and heterogeneous catalysis, petrochemistry, and organometallic chemistry. a few components of the monograph may be of curiosity for experts in inorganic and natural chemistry, theoretical chemistry, biochemistry or even biology, and additionally in the event you paintings within the petrochemical undefined, business natural synthesis and biotechnology.
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Extra info for Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes
Example text
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. Thus, the methyllutetium which enters into an exchange reaction with 13 presents another case of C–H bond activation by high-valent metal complex [13]. Ion metalates arenes similarly to palladium(II). However, unlike palladium(II) ' complexes of Pt(IV) are stable compounds and have been isolated [14]. The ion easily platinates arenes under the action of light [14] (or [14]) giving the first example of photo-electrophilic substitution of arenes.
The latter formula gives non-linear dependence of activation energy on the reaction’s enthalpy; whereas, less precise Polanyi-Semenov rule predicts a linear dependence: Nevertheless, the thermodynamics of these reactions remain an important basis for their kinetic characteristics. Polar factors, while they should not be completely neglected, are not of great importance in reactions of neutral free radicals with molecules. If we have a series of substrates reacting via C–H homolytic cleavage, we can then expect that as a rule, the stronger the C–H bond, the smaller the rate constant.
J. Chem. , Perkin Trans. 2. 1972, 2247. (f) Garnett, J. ; Long M. ; Peterson, K. B. Aust. J. Chem. 1974, 27, 1823. (g) Grigoryan E. ; D’ychkovskiy, F. ; Mullagaliev, I. R. Dokl. Akad. Nauk SSSR 1975, 224, 859 (in Russian). 12. 13. ; Felkin, H. J. Chem. , Chem. Commun. 1980, 1243. (b) Crabtree, R. ; Mihelcic, J. ; Quirk, J. M. J. Am. Chem. Soc. 1979, 101, 7738. (c) Janowicz, A. ; Bergman, R. G. J. Am. Chem. Soc. 1982, 104, 352. (d) Hoyano, J. ; Graham, W. A. , J. Am. Chem. Soc. 1982, 104, 3723. (e) Fendrick, C.
Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes by A.E. Shilov, Georgiy B. Shul'pin, Alexander E. Shilov
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