Rare-earth metal and actinide organoimide chemistry

The chemistry of actinide (An) and rare-earth metal (Ln and group 3) complexes featuring multiple bonding interactions with main-group fragments has witnessed an enormous growth since the first mentioning in the mid-eighties and apparent stagnation in the nineties. The recent surge of interest is particularly owing to our eagerness to acquire a fundamental understanding of the chemical bonding properties of such long-time elusive compounds but also the potential emergence of unprecedented reactivity in organic or inorganic transformations. Contrary to uranium imide chemistry, traditional and routine synthesis protocols seem less viable for rare-earth metal imide complexes. The present review puts its main emphasis on identifying reaction pathways currently available/elaborated for the generation of [An&z.dbd;NR] and [Ln&z.dbd;NR] moieties. We also address the intriguing structural and reactivity features of such organoimide derivatives as highlighted by small-molecule activation, group-transfer capability, and the redox chemistry of uranium, cerium, ytterbium, samarium and europium. Elaborate synthesis schemes pave the way to f-element and group 3 complexes with multiply bonded imido ligands displaying intriguing reactivity.