Density functional theory, DFT, calculations were carried out on complexes containing cyclopentadienyl anions and lithium or sodium cations; half-sandwich, sandwich and sandwich-like complexes (among them triple-decker ones) are analyzed. Searches performed through the Cambridge Structural Database revealed that crystal structures containing these motifs exist, mostly structures with sodium cations. The DFT calculations performed here include geometry optimization and frequency calculations of the complexes at the ωB97XD/aug-cc-pVTZ level, followed by the partitioning of the energy of interaction via the Energy Decomposition Analysis scheme, EDA, at the BP86-D3/TZ2P level. Additional calculations and analyses were performed using both the Quantum Theory of Atoms in Molecules, QTAIM, and the Natural Bond Orbital analyses, NBO. The results of this work show that the electrostatic interaction energy is the most important attractive contribution to the total interaction energy of each of the complex systems analyzed here, and that complexation itself leads to minor electron charge shifts.
Keywords: DFT calculations; sandwich complex; triple-decker complex.