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Updated: Jan 24, 2026

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Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido
Thibault Cheisson1, Kyle D Kersey1, Nolwenn Mahieu1,2
1P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
Abstract:
A series of thorium(IV)-imido complexes was synthesized and characterized. Extensive experimental and computational comparisons with the isostructural cerium(IV)-imido complexes revealed a notably more covalent bonding arrangement for the Ce═N bond compared with the more ionic Th═N bond. The thorium-imido moieties were observed to be 3 orders of magnitude more basic than their cerium congeners. More generally, these results provide unique experimental evidence for the larger covalent character of 4f05d0 Ce(IV) multiple bonds compared to its 5f06d0 Th(IV) actinide congener.
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