Contrasting Behavior of the Z Bonds in X-Z···Y Weak Interactions: Z = Main Group Elements Versus the Transition Metals.

In contrast to the increasing family of weak intermolecular interactions in main-group compounds (X-Z···Y, Z = main-group elements), an analysis of the Cambridge Structural Database indicates that electron-saturated (18-electron) transition-metal complexes show reluctance toward weak M bond formation (X-M···Y, M = transition metal). In particular, weak M bonds involving electron-saturated (18-electron) complexes of transition metals with partially filled d-orbitals are not found. We propose that the nature of valence electron density distribution in transition-metal complexes is the primary reason for this reluctance. A survey of the interaction of selected electron-saturated transition-metal complexes with electron-rich molecules (Y) demonstrates the following: shielding the possible σ-hole on the metal center by the core electron density in 3d series, and enhanced electronegativity and relativistic effects in 4d and 5d series, hinders the formation of the M bond. A balance in all the destabilizing effects has been found in the 4d series due to its moderate polarizability and primogenic repulsion from inner core d-electrons. A changeover in the donor-acceptor nature of the metal center toward different types of incoming molecules is also unveiled here. The present study confirms the possibility of M bond as a new supramolecular force in designing the crystal structures of electron-saturated transition-metal complexes by invoking extreme ligand conditions.