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

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 reports and systematizes the chemistry of steel ion activation of alkenes and alkynes. The e-book provides the migration of ? bonds; the oxo response; and the hydrosilation of alkenes and alkynes. The textual content additionally covers subject matters at the oxidation of alkenes and alkynes, in addition to the a number of insertion reactions of alkenes and alkynes.

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Example text

Carbon monoxide insertion in the alkylcobalt tricarbonyl forms an acylcobalt tricarbonyl in equilibrium with alkylcobalt tetracarbonyl. It was assumed that in the last step the coordinatively unsatured acylcobalt Co2(CO)8 + H2 , 124 HCo(CO)4 , 2 HCo(CO)4 125 (76) HCo(CO)3 + CO (81) 126 HCo(CO)3 + RCH=CH 2 ► RCH2CH2Co(CO)3 (82) RCH2CH2Co(CO)3 + CO ► RCH2CH2COCo(CO)3 (83) ► RCH2CH2CHO + HCo(CO)3 (84) RCH2CH2COCo(CO)3 + H2 tricarbonyl (in preference to alkylcobalt tetracarbonyl) reacts with molecular hydrogen to form the products and regenerate the catalyst, HCo(CO)3.

The complexes l,2,6-tris(pyridine)-Rh(III) chloride and Rh2Cl2(SnCl2 · C2H5OH)4 are effective catalysts [78] for the oxo reaction of alkenes in ethanol solutions. Iron pentacarbonyl, Fe(CO)5, functions as a catalyst at temperatures above 180°C, and is accordingly used in the reduction of aldehydes to alcohols under hydroformylation conditions. Nickel tetracarbonyl, Ni(CO)4, is unreactive and therefore unsuitable as an oxo catalyst. Catalyst concentration plays an important part in determining the rate of the oxo reaction and the distribution of isomers obtained.

Evidence pertaining to the dissociation of dicobalt octacarbonyl is provided by the catalytic effect of pyridine and pyridine homologs on the rate of the oxo reaction when added in small quantities. In the presence of a molar quantity of pyridine equal to that of the catalyst, the rate of the oxo reaction is doubled [123,124]. The more basis aliphatic tertiary amines, such as triethylamine and tributylamine, however, cause a reduction of the rate. The catalytic effect of small quantities of pyridine was explained by Iwanaga [123] on the basis of a pre-equilibrium step involving formation of a Co2(CO)8base complex and subsequent reaction of this complex with hydrogen to form HCo(CO)4, as indicated in reactions (86) and (87).

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


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