Download PDF by M. M. Taqui Khan: Activation of Alkenes and Alkynes

By M. M. Taqui Khan

ISBN-10: 0124061028

ISBN-13: 9780124061026

ISBN-10: 0323160166

ISBN-13: 9780323160162

Homogeneous Catalysis by means of steel Complexes, quantity II: Activation of Alkenes and Alkynes stories 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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Extra resources for Activation of Alkenes and Alkynes

Example text

The movement of deuterium at each step of the II. 5 + CHD=CD—(CH 2 ) 2 —CH 3 (CH2)2 CH3 CH3CH2CH2CD=CDH CH3CH2CH2CD=CDH (32) CH 15 D 15 I K CH I CH2 I CH3 ■MH -► CH3CH2CH—CD—CH2D (33) > CH3CH2CH=CH—CD2H (34) reaction has been followed by NMR spectrometric measurement of the vinylic and allylic protons. The observed isotope distribution supports the alkyl reversal mechanism for stepwise migration of the double bond, as indicated in Eq. (32), since the 7r-allyl mechanism would also place some label on carbon atom 3.

58). RCH 2 CH 2 CHO R C H = C H 2 + CO + H 2 "etalcarbonyl ^ (58) RCH(CHO)CH 3 The oxo reaction is catalyzed by a variety of metal carbonyls and other complexes, such as cobalt carbonyls [74], rhodium carbonyls [75], iron and manganese carbonyls [76], bis(triphenylphosphine)rhodium(I) [77,78], and hydridocarbonyltris(triphenylphosphine)rhodium(I) [79,80]. The primary products of hydroformylation of olefins are aldehydes, which can be converted readily to secondary products such as primary alcohols by subsequent hydrogénation reactions.

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.

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

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