Download e-book for kindle: Activation of Alkenes and Alkynes by M. M. Taqui Khan

By M. M. Taqui Khan

ISBN-10: 0124061028

ISBN-13: 9780124061026

ISBN-10: 0323160166

ISBN-13: 9780323160162

Homogeneous Catalysis through steel Complexes, quantity II: Activation of Alkenes and Alkynes experiences and systematizes the chemistry of steel ion activation of alkenes and alkynes. The booklet provides the migration of ? bonds; the oxo response; and the hydrosilation of alkenes and alkynes. The textual content additionally covers themes at the oxidation of alkenes and alkynes, in addition to the a number of insertion reactions of alkenes and alkynes.

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The products of isomerization were analyzed by vapor-phase chromatography and NMR spectra. Since on using CH3COOD along with the palladium(I) catalyst it was found [57] that deuterium is not incorporated in the isomerized olefin, it was concluded that hydrogen is not lost from the substrate hydrocarbon at any stage, and the mechanism thus seems to be intramolecular without participation of the solvent. The formation of palladium hydride intermediates in palladium(II) catalysis was questioned [57] on the basis of nondetectability of such intermediates by NMR.

2) One deuterium is introduced for each molecule of 1-butène that is isomerized to eis- and /rúra-2-butenes. (3) The rate of isomerization/deuteration varies with the catalyst. , H 2 Fe(CO) 4 ] catalysts, the rate of isomerization is much faster than that of deuteration. Observations 1-3 may be explained by reaction scheme (37). The metal ion in the olefin π complex 61 is oxidized by D + (or H + ) in step kx to form the hydrido complex 62 which on rearrangement forms the σ complex 63. Complex 63 then rearranges to the hydridometal-olefin complex 64, which undergoes an olefin displacement reaction with 1-butène to release 2-deutero-l-butène, CH 2 =CDC 2 H 5 , in solution.

Hydroformylation of olefin oxides results in the formation of hydroxy aldehydes. Propylene oxide [101], 113, undergoes hydroformylation between 80° and 100°C in the presence of cobalt octacarbonyl to give ß-hydroxy-«butyraldehyde, 114, as the major product [Eq. (64)]. The temperature range of this reaction is critical. Below 80°C no appreciable reaction takes place, whereas above 100°C propylene oxide isomerizes to acetone which undergoes subsequent side reactions. Ethylene oxide probably undergoes a similar 45 II.

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Activation of Alkenes and Alkynes by M. M. Taqui Khan


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