Mono(imidazolin-2-iminato) Actinide Complexes: Synthesis and Application in the Catalytic Dimerization of Aldehydes

The synthesis of the mono(imidazolin-2-iminato) actinide(IV) complexes [(Im(R)N)An(N{SiMe3)(2)}(3)] (3-8) was accomplished by the protonolysis reaction between the respective imidazolin-2-imine (Im(R)NH, R = tBu, Mes, Dipp) and the actinide metallacycles [{(Me3Si)N}(2)An{kappa C-2,N-CH2SiMe2N(SiMe3)}] (1, An = U; 2, M = Th). The thorium and uranium complexes were obtained in high yields, and their structures were established by single-crystal X-ray diffraction analysis. The mono(imidazolin-2-iminato) actinide complexes 3-8 display short An-N bonds together with large An-N-C angles, indicating strong electron donation from the imidazolin-2-iminato moiety to the metal, corroborating a substantial p-character to the An-N bond. The reactivity of complexes 3-8 toward benzaldehyde was studied in the catalytic dimerization of aldehydes (Tishchenko reaction), displaying low to moderate catalytic activities for the uranium complexes 3-5 and moderate to high catalytic activities for the thorium analogues 6-8, among which 8 exhibited the highest catalytic activity. In addition, actinide coordination compounds showed unprecedented reactivity toward cyclic and branched aliphatic aldehydes in the catalytic Tishchenko reaction mediated by the thorium complex [(Im(Dipp)N)Th{N(SiMe3)(2)}(3)] (8), exhibiting high activity even at room temperature. Moreover, complex 8 was successfully applied in the crossed Tishchenko reaction between an aromatic or polyaromatic and an aliphatic cyclic and branched aldehyde, yielding selectively the asymmetrically substituted ester in high yields (80-100%).