Abstract
The rate of hydrogenation of cyclohexene catalyzed by RhCl(PPh 3) 3 was studied in the presence of BCl 3, B(CH 3) 3, Eu(fod) 3 (fod = 6,6,7,7,8,8-heptafluoro-2,2-dimethyl-3,5-octadione anion), AlCl 3, AlBr 3 and Al(i-C 4H 9) 3. Only AlBr 3 effected a large increase in rate, which is attributed to the formation of the more active catalyst RhBr(PPh 3) 3 by a simple metathesis. A very significant rate enhancement was found for the hydrogenation of ethylene by RhCI(PPh 3) 3 when Al(i-C 4H 9) 3 was added to the system. It is postulated that RhH(PPh 3) 3 formation is responsible for this rate increase. The rate of 1-hexene hydrogenation catalyzed by RuCl 2(PPh 3) 3 is increased by the presence of aluminum alkyls, and the origin of this rate increase is elucidated. In the course of this work the compound RuCl(CH 3)(PPh 3) 3 was isolated and characterized. This compound is closely related to alkyl complexes which have been postulated as intermediates in olefin hydrogenation catalysis by RuClH(PPh 3) 3.
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