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Kinetic and mechanistic investigation of the sequential hydrogenation of phenylacetylene catalyzed by rhodium (I) phosphine complexes of the type [Rh(η2-O2Z)(PR3)2]

✍ Scribed by U. Möhring; M. Schäfer; F. Kukla; M. Schlaf; H. Werner

Book ID
103997466
Publisher
Elsevier Science
Year
1995
Tongue
English
Weight
708 KB
Volume
99
Category
Article
ISSN
1381-1169

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✦ Synopsis

Chelate complexes of the type [ Rh( q2-0,Z) (PR,),] (Z = CCH,, CCF3, CtBu, S( 0) -p-C&I&H,;

PR, = PiPr,, PPhiPr,, PPh,iPr) catalyze the hydrogenation of phenylacetylene in toluene solution at 60°C. Selectivities close to 100% are achieved for the hydrogenation of the alkyne to the alkene in the presence of the acetate and trifluoroacetate complexes [ Rh( $-0,CR) (PiPr,),] (R = CH3 1, CF, 2). However, in other cases the reduction of the C-C double bond is also observed. In general, the selectivity of the hydrogenation reaction depends both on the phosphine and the anionic ligand. For the reduction of PhC=CH catalyzed by 1, the addition of acetic acid leads to a dramatic decrease in the catalytic activity.

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