By R. S. Coffey (auth.), Renato Ugo (eds.)
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Extra resources for Aspects of Homogeneous Catalysis: A Series of Advances Volume 1
Wilkinson has suggested that at low concentrations further dissociation occurs according to (50), and that RhCl(PPh3) is a more active RhCl(PPh3)2 ~ RhCl(PPh3) + PPh3 (50) catalytic intermediate than RhCl(PPh3)2 . 5C4HsO]n when kept under nitrogen . 6 M IN BENZENE '. 0 ap Figure 4. Hydrogenation of hex-l-ene. Under rather different reaction conditions (amino phosphine ligands, styrene (4 parts), benzene (1 part) at 40oC, and 1 atm. of hydrogen) Stem et al. have found the dependence of rate on catalyst concentration varies between zero and first order as the concentration decreases .
PREPARATION OF CATALYSTS Several groups working independently appear to have synthesised RhCl(PPha)s during the period 1964-1965 [76-80], and some quickly noted it was an excellent hydrogenation catalyst at room temperature and pressure [76, 77, 81]. Previously RhCl(PHPh2)a had been prepared from [RhCl(C2H4)2]2 via reaction (42)  and various phosphite analogues RhX(P(OR)s)a had been known a long time . Refiuxing an ethanolic solution of RhC1a3H20 with six molar equivalents of triphenylphosphine gives RhCl(PPhs)s in almost quantitative yield (18], the phosphine being the reducing agent (18, 79].
3), but allyl esters can be reduced without hydrogenolysis . The catalyst is particularly good for hydrogenation of certain cyclic dienes, which isomerise or disproportionate with heterogeneous catalysts and give aromatic compounds. Thus dihydrotetralins and isotetralin can be reduced to octalins in very high yield  (see Table 9). Because the catalyst can operate under conditions where little isomerisation occurs, and the addition of two hydrogen atoms occurs simultaneously or the second hydrogen adds extremely rapidly, RhCI(PPha)a is useful in preparing compounds labelled with deuterium at specific positions.