Tris rhodium chloride, homogeneous hydrogenation

Many catalysts, certainly those most widely used such as platinum, palladium, rhodium, ruthenium, nickel, Raney nickel, and catalysts for homogeneous hydrogenation such as tris(triphenylphosphine)rhodium chloride are now commercially available. Procedures for the preparation of catalysts are therefore described in detail only in the cases of the less common ones (p. 205). Guidelines for use and dosage of catalysts are given in Table 1. 

Reduction of the double bond only was achieved by catalytic hydrogenation over palladium prepared by reduction with sodium borohydride. This catalyst does not catalyze hydrogenation of the aldehyde group [31]. Also sodium borohydride-reduced nickel was used for conversion of cinnamaldehyde to hydrocinnamaldehyde [31]. Homogeneous hydrogenation over tris(triphenylphosphine)rhodium chloride gave 60% of hydrocinnamaldehyde and 40% of ethylbenzene [5(5]. Raney nickel, by contrast, catalyzes total reduction to hydrocinnamyl alcohol [4S. Total reduction of both the double... 

Hydrogenation of phthalic anhydride over copper chromite afforded 82.5% yield of the lactone, phthalide, and 9.8% of o-toluic acid resulting from hydrogenolysis of a carbon-oxygen bond [1015]. Homogeneous hydrogenation of a,a-dimethylsuccinic anhydride over tris(triphenylphos-phine)rhodium chloride gave 65% of a,a-dimethyl- and 7% of )S,)S-dimethyl-butyrolactone [1016]. 

In the early papers (26, 17) on homogeneous hydrogenation by tris(triphenylphosphine)rhodium(I) chloride, Wilkinson and coworkers found the kinetic isotope effect for deuterium addition to be... 

Hydrogenation of olefins on a soluble catalyst has been reported recently [61,62]. Tris(triphenylphosphine)rhodium chloride [(Ph3P)3RhCl] will promote homogeneous hydrogenation of reactive double bonds, including the A -bond in Ai -dien"3-ones, where the product of deuteration was the ia,2a-dideutero-compound (17) [62]. The mechanism is not... 

Heterogeneous catalysis (Pd) in tritiation of l,4-dien-3-ones leads mainly to l) -tritiation (ca. 76%). Tritium distribution studies indicate that the reaction is probably a 1,4-addition of tritium onto the more exposed p-face of the dienone, which is tilted downwards with respect to ring b (211). Homogeneous catalysis with tris(triphenylphosphine)rhodium chloride, however, is known to favour la-tritiation. Similarly, homogeneous hydrogenation of the less reactive... 

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