Its Environment Engraves the Geometry of a Molecular Entity: Allyl Coordination within a Dicationic Ruthenium(IV) Complex

The best molecular arrangements for [Ru(η5-C5(CH5)5)(η3-CH2CHCHC6H5)(CH3CN)2]2+ (1) in various environments are determined. The isolated compound 1a serves as a point of reference. On the basis of crystal structure data, solid-state environments are modeled by first placing the cationic compound into the appropriate anionic environment 2a and then completing the unit cell contents by addition of the solvent molecule 3a. Density functional calculations (BP86) augmented by various dispersion corrections (BP86-D2, BP86-D3, BP86-D3(BJ), BP86-dDsC) establish the computational approach for electronic structure and geometry optimization. According to the models considered, intermolecular electrostatic interactions are to a major part responsible for substantial changes in intramolecular arrangements.