Organoactinides in catalysis

During the last three decades, organoactinide chemistry has flourished, reaching a high level of sophistication. The use of organoactinide complexes as stoichiometric or catalytic compounds to promote synthetically important organic transformation has grown-up due to their rich, complex, unique and highly informative organometallic chemistry. In many instances the regio- and chemo-selectivities displayed by organoactinide complexes are complementary to those observed for other transition-metal complexes. The reactivity of organoactinide complexes is based on their ability to perform unique bond-breaking and bond-forming reactions of distinct moieties. The factors influencing such processes are the steric and electronic effects. This review is aimed at a brief and selective survey of the catalytic chemistry of organoactinide complexes in homogeneous and heterogeneous catalytic reactions. A comprehensive review for the reactivities of actinide compounds has been published covering the literature until 1992. This review covers the new literature of the last decade, and will focus on the reactivity of organoactinide complexes as catalysts for demanding organic transformations. In the beginning the synthesis and characterization of organoactinide based complexes and catalysts will be presented, followed by a survey of organic transformation catalyzed by these organoactinides, including oligomerization, dimerization, hydrosilylation and hydroamination of terminal alkynes, coupling of isonitriles with terminal alkynes, polymerization of alpha-olefins, heterogeneous hydrogenation of arenes and more. For each reaction, the scope, kinetic, thermodynamic and mechanistic aspects are presented. (c) 2006 Elsevier B.V. All rights reserved.