By A.E. Shilov, Georgiy B. Shul'pin, Alexander E. Shilov
This monograph is dedicated to the activation and diverse alterations of saturated hydrocarbons (alkanes), i.e. reactions followed through the C--H and C--C bond cleavage. Alkanes are the most components of oil and average fuel, and as a result are the crucial feedstocks for the chemical undefined. nonetheless, those elements are recognized to be the least reactive natural compounds. unique recognition 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 ebook, the activation of C--H bonds in arenes or even olefins and acetylenes are thought of. The monograph might be worthwhile not just in the event you have an interest in the activation of alkanes and different hydrocarbons through 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 case you paintings within the petrochemical undefined, commercial natural synthesis and biotechnology.
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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].
The alkane transformations described here should be taken into consideration for comparison when discussing the metal complex activation. II. 1. T RANSFORMATIONS U NDER THE A CTION OF H EAT OR I RRADIATION Under the action of heat or irradiation, alkanes decompose to produce free radicals which further form stable products. Such processes, especially pyrolysis, are of practical importance. II. A. PYROLYSIS Heating alkanes [la-c] at temperature 900-2000 °C gives rise to the formation of radicals: 21 22 CHAPTER II (Refs.
Davidson, J. M. J. Chem. Soc.. 1965, 843. ; Verberg, G. Recl. Trav. Chim. Pays-Bas 1965, 84, 1263. ; Danno, S. et al. J. Am. Chem. Soc. 1969, 91, 7166. (c) Garnett, J. ; Hodges, R J. J. Am. Chem. Soc. 1967, 89, 4546. 19 20 References for Chapter I 10. Gol’dshleger, N. ; Tyabin, M. ; Shilov, A. ; Shteinman, A. 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.