Conrad A P Goodwin, Ralph W Adams, Andrew J Gaunt, Susan K Hanson, Michael T Janicke, Nikolas Kaltsoyannis, Stephen T Liddle, Iain May, Jeffrey L Miller, Brian L Scott, John A Seed, George F S Whitehead
Comparison of bonding and electronic structural features between trivalent lanthanide (Ln) and actinide (An) complexes across homologous series' of molecules can provide insights into subtle and overt periodic trends. Of keen interest and debate is the extent to which the valence f- and d-orbitals of trivalent Ln/An ions engage in covalent interactions with different ligand donor functionalities and, crucially, how bonding differences change as both the Ln and An series are traversed. Synthesis and characterization (SC-XRD, NMR, UV-vis-NIR, and computational modeling) of the homologous lanthanide and actinide N-heterocyclic carbene (NHC) complexes [M(C5 Me5 )2 (X)(IMe4 )] {X = I, M = La, Ce, Pr, Nd, U, Np, Pu; X = Cl, M = Nd; X = I/Cl, M = Nd, Am; and IMe4 = [C(NMeCMe)2 ]} reveals consistently shorter An-C vs Ln-C distances that do not substantially converge upon reaching Am3+ /Nd3+ comparison...
April 3, 2024: Journal of the American Chemical Society