Recent developments in highly basic N-heterocyclic iminato ligands in actinide chemistry.

Abstract

In the last decade, major conceptual advances in the chemistry of actinide molecules and materials have been made to demonstrate their distinct reactivity profiles as compared to lanthanide and transition metal compounds, but some difficult questions remain concerning the intriguing stability of low-valent actinide complexes, and the importance of the 5f-orbitals in reactivity and bonding. The imidazolin-2-iminato moiety has been extensively used in ligands for the advancement of actinide chemistry owing to its unique capability of stabilizing the reactive and highly electrophilic metal ions by virtue of its strong electron donation and steric tunability. The current review article describes recent developments in the chemistry of light actinide metal ions (thorium and uranium) bearing these N-heterocyclic iminato moieties as supporting ligands. In addition, the effect of ring expansion of the N-heterocycle on the catalytic aptitude of the organoactinides is also described herein. The synthesis and reactivity of actinide complexes bearing N-heterocyclic iminato ligands are presented, and promising apposite applications are also presented. The current review focuses on addressing the catalytic behavior of actinide complexes with oxygen-containing substrates such as in the Tishchenko reaction, hydroelementation processes, and polymerization reactions. Actinide complexes have also found new catalytic applications, as demonstrated by the potent chemoselective carbonyl hydroboration and tandem proton-transfer esterification (TPTE) reaction, featuring coupling between an aldehyde and alcohol.