Crabtree's catalyst

[4] Crabtree’s catalyst is effective for the hydrogenations of mono-, di-, tri-, and tetra-substituted substrates.

The catalyst is tolerant of weakly basic functional groups such as ester, but not alcohols (see below) or amines.

[6] The catalyst becomes irreversibly deactivated after about ten minutes at room temperature, signaled by appearance of yellow color.

More specifically, it catalyzes the direct exchange of a hydrogen atom with its isotopes deuterium and tritium, without the use of an intermediate.

With palladium on carbon in ethanol the product distribution is 20:80 favoring the cis isomer (2B in Scheme 1).

This is due to slight haptophilicity, an effect in which a functional group binds to the surface of a heterogeneous catalyst and directs the reaction.

Crabtree and graduate student George Morris discovered this catalyst in the 1970s while working on iridium analogues of Wilkinson's rhodium-based catalyst at the Institut de Chimie des Substances Naturelles at Gif-sur-Yvette, near Paris.

Crabtree's catalyst
Crabtree's catalyst
Crabtree's catalyst is thought to operate via an intermediate such as this: cis -[IrH 2 (cod)L 2 ] (cationic charge not shown).
An example of isomerization with Crabtree's catalyst. The reaction proceeds 98% to completion in 30 minutes at room temperature.
Directing effect of an –OH group on diastereoselectivity of hydrogenation by Crabtree's catalyst. Hydrogen is added from the direction of the iridium atom, selecting for the reactivity shown above. Additional ligands on catalyst not shown.