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By M.M. Taqui Khan

Activation Of Small Inorganic Molecules

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The mechanism of hydrogénation with these ruthenium(II) catalysts thus seems to be similar to the proposed by Halpern and James [156,164]. Jardine and McQuillin [165] reported the hydrogénation in methanol solution of cyclopentene, cyclohexene, cyclooctene, and diphenylacetylene with tris(triphenylphosphine)chlorohydridoruthenium(II) as the catalyst. Except for diphenylacetylene (which gave c/s-stilbene), these substrates gave saturated products. The catalyst was formed in situ by the treatment of ruthenium trichloride with triphenylphosphine in methanol.

178] have reported catalysis by tris(diethyl sulfide)trichlororhodium(III), RhCl 3 (SEt 2 ) 3 , in Λ^,Λ^-dimethylacetamide for the hydrogénation of ethylene and substituted ethylenes. It may be recalled (p. 48) that (PPh 3) 3RhCl is ineffective for the hydrogénation of ethylene because of the formation of a very stable olefin complex. The replacement of the tertiary phosphines by alkyl sulfides in the coordination sphere of rhodium thus alters to a considerable extent its catalytic properties.

Kinetic studies of the hydrogénation of alkenes and alkynes were conducted by the addition of the solid catalyst RhCl(PPh 3 ) 3 to a 1:1 benzene-ethanol solution saturated with hydrogen and followed by the addition of the unsaturated compound. This order of addition of catalyst to the solution ensures better dissolution of the catalyst without dimerization to [RhCl(PPh 3 ) 2 ] 2 . The solution is maintained saturated with respect to hydrogen at all times. The addition of a polar solvent such as ethanol or a ketone to benezene sufficiently accelerates the rate of hydrogénation, although no correlation could be found between the dielectric constant of the polar solvent (co-catalyst) and the reaction rate.

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