In the family of metallocenes, MgCp∗2 (Cp∗ = pentamethylcyclopentadienyl) exhibits a regular linear sandwich structure, whereas CaCp∗2 is bent in both the gas phase and solid state. Bending is typically observed for metal ions which possess a lone pair. Here, we investigate which electronic differences cause the bending in complexes lacking lone pairs at the metal atoms. The bent gas-phase geometry of CaCp∗2 suggests that the bending must have an intramolecular origin. Geometry optimizations with and without dispersion effects/d-type polarization functions on MCp2 and MCp∗2 gas-phase complexes (M = Ca, Mg) establish that attractive methyl⋯methyl London dispersion interactions play a decisive role in the bending in CaCp∗2. A sufficient polarizability of the metal to produce a shallow bending potential energy curve is a prerequisite but is not the reason for the bending. Concomitant ligand-induced charge concentrations and localizations at the metal atoms are studied in further detail, for which real-space bonding and orbital-based descriptors are used. Low-temperature crystal structures of MgCp∗2 and CaCp∗2 were determined which facilitated the identification and characterization of intermolecular pseudo-pregostic interactions, C-H⋯Ca, in the CaCp∗2 crystal structure.