Theoretical insights into the chemical bonding in actinide complexes

•Recent developments in theoretical tools for bonding analysis.•Features of the actinide ligand bond.•Quantum chemical topology and energy decomposition analysis to understand bent thorocene complexes structures.

The chemical bonding in actinide compounds is usually analyzed by inspecting the shape and the occupation of the orbitals or by calculating bond orders which are based on orbital overlap and occupation numbers. However, this may not give a definite answer because the choice of the partitioning method may strongly influence the result leading sometimes to qualitatively different answers. This review highlights that the joint and complementary tools such as charge, orbital, quantum chemical topology and energy decomposition analyses are very powerful to understand chemical bonding in the field of actinide chemistry. However, understanding the actinide–ligand bond is not straightforward and requires caution in the use of these methods. This review is illustrated through applications to newly discovered bent actinocene compounds and actinide endohedral clusters fulfilling a 32-electron rule.

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