Key questions for
the study of chemical bonding in actinide compounds
are the degree of covalency that can be realized in the bonds to different
donor atoms and the relative participation of 5f and 6d orbitals.
A manifold of theoretical approaches is available to address these
questions, but hitherto no comprehensive assessments are available.
Here, we present an in-depth analysis of the metal–ligand bond
in a series of actinide metal–organic compounds of the [M(salen)2] type (M = Ce, Th, Pa, U, Np, Pu) with the Schiff base N,N′-bis(salicylidene)ethylenediamine
(salen). All compounds except the Pa complex (only included in the
calculations) have been synthesized and characterized experimentally.
The experimental data are then used as a basis to quantify the covalency
of bonds to both N- and O-donor atoms using simple electron-density
differences and the quantum theory of atoms in molecules (QTAIM) with
interacting quantum atoms. In addition, the orbital origin of any
covalent contributions was studied via natural population analysis
(NPA). The results clearly show that the bond to the hard, charged
O-donor atoms of salen is consistently not only stronger but also
more covalent than bonds to the softer N-donor atoms. On the other
hand, in a comparison of the metals, Th shows the most ionic bond
character even compared to its 4f analogue Ce. A maximum of the covalency
is found for Pa or Np by their absolute and relative covalent bond
energies, respectively. This trend also correlates with a significant
f- and d-orbital occupation for Pa and Np. These results underline
that only a comprehensive computational approach is capable of fully
characterizing the covalency in actinide complexes.