Emergence of comparable covalency in isostructural cerium(IV)- and uranium(IV)-carbon multiple bonds

The chemical bonding of actinide and transition metal cations is known to exhibit variable levels of covalency, whereas that of the lanthanides is characterised as overwhelmingly ionic like alkali and alkaline earth metals. Here, we report a structural, spectroscopic, magnetic, and computational study of the iso-structural carbene complexes [M(BIPMTMS)(ODipp)2] [M = Ce (1), U (2), Th (3); BIPMTMS = C(PPh2NSiMe3)2; Dipp = C6H3-2,6-Pri 2]. In order to avoid the deficiencies of orbitalbased theoretical treatments we probed the bonding of 1-3 with a RASSCF density-based approach that explicitly treats the orbital energy near-degeneracy and overlap contributions to covalency. For these complexes unexpected similar levels of covalency are found for cerium(IV) and uranium(IV), whereas thorium(IV) is found to be more ionic. This trend is found in all computational methods employed and is reproduced in experimental covalency-driven exchange reactions of 1-3 with MCl4 salts (M = Ce, U, Th).