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DFT modeling of sandwich complexes involving cationic palladium chains and polyenic or polycyclic aromatic hydrocarbons.

DFT calculations are reported on a series of one-dimensional palladium complexes with general formula [Pd(m)(C(2n)H(2n+2))(2)](2+) (m = 2-4, n = 2-8, n > or = m), in order to model and analyze the bonding in the series of organometallic sandwich compounds recently reported by the group of T. Murahashi and H. Kurosawa. The bonding interactions are elucidated, and the frontier orbitals involved are described as a function of the haptotropic conformation of the metal atoms, either di-hapto or tri-hapto. In both cases, the driving force to the complex organization is a strong donation interaction from the pi system of the hydrocarbons to an orbital with appropriate phase and composition, delocalized over the metal chain, and depopulated by the double oxidation process. No net bonding interaction can be characterized along the metal string, and the metal-metal distances are mainly governed by the hapticities of adjacent atoms. The energy associated with the formation of a complex is calculated with respect to its fragments, assumed either isolated or solvated. The results emphasize the stabilizing role of a large delocalization of the positive charge transferred to the hydrocarbons. This delocalization extends to the hydrocarbon regions not directly in contact with palladium and highlights the importance of these "inactive" regions in complexes made from diphenyl polyenes or polycyclic aromatic hydrocarbons. Finally, the bonding pattern deduced from calculations has been utilized to consider the feasibility of novel sandwich architectures, whose computed energy balance eventually proves similar to that of already existing compounds.