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In this critical review we summarize the latest results obtained during the last decade concerning the catalytic activities of organoactinide complexes. We begin with a brief summary of the synthesis and characterization of uranium and thorium complexes that later will be used as catalysts for demanding chemical transformations. Hydroamination, hydrosilylation of terminal alkynes, coupling of terminal alkynes with isonitriles, catalytic reduction of azides and hydrazines, ring opening polymerization of cyclic esters and polymerization of alpha-olefins are covered in this review (118 references). The topics covered in this review regarding organoactinide chemistry will be of interest to inorganic, organic and organometallic chemists, material and catalytic scientists due to its unique mode of activation as compared to late transition-metals. In addition, the field of organoactinide complexes in catalysis is steadily growing, because of the complementary reactivity of organoactinides as compared to other early or late transition complexes, in demanding chemical transformations.

The coupling reaction of terminal alkynes and tert-butylisonitrile to yield substituted alpha,beta-acetylenic aldimines is catalyzed by the organoactinide neutral complexes Cp*2AnMe2 (Cp* = C5Me5, An = Th, U) and the cationic complex [(Et2N)3U][BPh4]. The reaction proceeds by a 1,1-insertion of the isonitrile into the metal-acetylide bond. Additional insertion products can be obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is presented, in addition to the crystal structure of Cp*2UMe2