Covalency in AnCp4 (An = Th-Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses

Dalton Transactions : an International Journal of Inorganic Chemistry
Matthew J Tassell, N Kaltsoyannis

Abstract

The geometric and electronic structures of the title compounds are calculated with scalar relativistic, gradient-corrected density functional theory. The most stable geometry of ThCp(4) (Cp = eta(5)-C(5)H(5)) and UCp(4) is found to be pseudo-tetrahedral (S(4)), in agreement with experiment, and all the other AnCp(4) compounds have been studied in this point group. The metal-Cp centroid distances shorten by 0.06 A from ThCp(4) to NpCp(4), in accord with the actinide contraction, but lengthen again from PuCp(4) to CmCp(4). Examination of the valence molecular orbital structures reveals that the highest-lying Cp pi(2,3)-based orbitals split into three groups of pseudo-e, t(2) and t(1) symmetry. Above these levels come the predominantly metal-based 5f orbitals, which stabilise across the actinide series, such that in CmCp(4), the 5f manifold is at more negative energy than the Cp pi(2,3)-based levels. The stability of the Cm 5f orbitals leads to an intramolecular ligand-->metal charge transfer, generating a Cm(III) f(7) centre and increased Cm-Cp centroid distance. Mulliken population analysis shows metal d orbital participation in the e and t(2) Cp pi(2,3)-based orbitals, which gradually decreases across the actinide series. By co...Continue Reading

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