14.3.5: Hydrogenation by Wilkinson's Catalyst

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Organometallic Compounds as Hydrogenation Catalysts

Migratory insertions play an important role in catalysis.

Figure \(\PageIndex{1}\): Mechanism of the Wilkinson hydrogenation catalyst (Attribution: Smokefoot / CC BY-SA (https://creativecommons.org/licenses/by-sa/4.0) https://commons.wikimedia.org/wiki/F...cleJMBrown.png)

For example a Rh-catalyst called the Wilkinson catalyst is an effective hydrogenation catalyst for olefins. The mechanism of the hydrogenation involves a combination of oxidative additions, olefin migratory insertions, and reductive eliminations (Fig. \(\PageIndex{1}\)). Wilkinson’s catalyst is the square planar chloro tris(triphenylphosphine) rhodium(I) complex. This molecule is actually a precatalyst that becomes the actual catalyst when it statistically loses a triphenylphosphine ligand producing chloro bis(triphenylphosphine) rhodium(I). The loss of this ligand is a reversible reaction, and thus the catalyst is in chemical equilibrium with the precatalyst. The actually catalyst is in a second chemical equilibrium with its dimer. The chloro bis(triphenylphosphine) rhodium(I) catalyst can undergo an oxidative addition in the presence of hydrogen to form a trigonal bipyramidal chlorodihydrido bis(triphenylphosphine) (III) rhodium complex. This species is in chemical equilibrium with an octahedral chlorodihydrido tris(triphenyl phosphine) rhodium(III) species that can form due to the presence of free triphenylphosphine ligands in the system. The trigonal bipyramidal species can then add an olefin that binds side-on to the Rh. Because the olefin is in cis-position to the hydride ligand it can undergo an olefin insertion. The Rh-C bond can either form with the first or the second carbon in the carbon chain of the olefin, giving a linear and a branched alkyl complex, respectively. The branched complex can undergo a β-hydride elimination thereby reforming the trigonal bipyramidal Rh-complex, and an olefin. This reaction is a side-reaction because the branched alkyl complex is sterically more crowded than the linear complex. The linear alkyl Rh complex can undergo a reductive elimination to form the linear alkane and the RhCl(PPh₃)₂ catalyst. This completes the catalytic cycle, and a new cycle can start.