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Read e-book online Activation of Small Inorganic Molecules PDF

By M.M. Taqui Khan

ISBN-10: 012406101X

ISBN-13: 9780124061019

ISBN-10: 0323150381

ISBN-13: 9780323150385

Activation Of Small Inorganic Molecules

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Mague and Wilkinson [172] have studied the catalytic properties of tris(triphenylarsine)chlororhodium(I) and tris(triphenylstibine)chlororhodium(I) in the catalytic hydrogénation of alkenes. The catalytic activities of these rhodium(I) complexes and of the related phosphine complex decrease in the order (PPh 3 ) 3 RhCl > (AsPh 3) 3RhCl > (SbPh 3) 3RhCl. The stibine complex was also the least stable of the three complexes. The cw-dihydridorhodium(III) complexes of triphenylarsine and triphenylstibine are nevertheless very stable with respect to the dissociation of hydride groups as compared to the triphenylphosphine complex, as indicated by the fact that bound hydrogen cannot be displaced by sweeping with nitrogen.

Cinnamate free radical can also react with [Co(CN) 5 ] " to give hydrocinnamylpentacyanocobaltate(III). The mechanism of Simandi and Nagy [143,144,146] differs from that of Kwiatek et al [123] in that the hydrogenerated substrate is formed through a free-radical intermediate. The proposal of a free-radical substrate intermediate by Simandi and Nagy [144] is based on the observation of Takahashi [150] that solutions of 3 Co(CN) 5 ~ saturated with hydrogen initiate radical polymerization. The reaction of pentacyanocobaltate(II) with the cinnamate free radical to form an organopentacyanocobaltate(II) is the chain-terminating step.

The formation of the ττ-allyl complex 25 requires that the conjugated diene should be able to assume a "cissoid" conformation. This conformation of the substrate is sterically 3 required to facilitate the formation of a ττ-allylic intermediate with Co(CN) 5 ~ prior to hydrogénation. At a high [CN~]/[Co] ratio, however, a a-Co(III) complex, 24, is formed 3 either directly from the diene and Co(CN) 5 H " or by the rearrangement of 38 1. ACTIVATION OF MOLECULAR HYDROGEN TABLE VI CONJUGATED AND ^ - U N S A T U R A T E D COMPOUNDS REDUCED BY HYDRIDOPENTACYANOCOBALTATE(III) Substrate CH 2—CH—CH—CH2 Product C H 3— C H 2— C H — C H 2 H 3C \ / c=c / \ References 128 H C H 2= C H — C ( C H 3) = C H 2 H CH3 C H 3— C H — C ( C H 3) = C H 2 C 6H 5C H = C H C O O H C H 3— C H = C H — C H = C H C O O H C6H5CH=CH2 C eH 5C ( C H 3) = C H 2 C 6H 5C ( C O O - ) = C H 2 C 6H 5C H = C H C H 2O H C H 2= C ( C H 3) C O O - C 6H 5C H 2— C H 2C O O H C H 3— C H = C H — C H 2— C H 2C O O H C6H5CH2—CH3 C 6H 5C H ( C H 3) — C H 3 C 6H 5C H ( C O O - ) — C H 3 C e H s C H 2C H 2C H 2O H C H 3— C H — C O O - 128,129, 146 129 128 128 128 128 128 1 C H 3C H = C H — C H O C H 3C H = C ( C H 3) — C H O C H 2= C — C O O " J C H 2C O O - 3 C H 3 C HC2H CH 2— C H O C H 3C H 2— C H ( C H 3) — C H O C H 3C H — c o o - 128 128 128 C H 2C O O " 128 128 C 6H 5C H 2— C — C O O H C 6H 5C H 2— C H — C O O H 129 ΝΟΗ C H 3— C — C O O H NH2 C H 3— C H — C O O H 129 II NOH I NH2 the τΓ-allyl complex 25 leading to the formation of 1-butene.

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Activation of Small Inorganic Molecules by M.M. Taqui Khan

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