Search for Osme Bonds with Systems as Electron Donors

The Osme bond is defined as pairing a Group 8 metal atom as an electron acceptor in a noncovalent interaction with a nucleophile. DFT calculations with the omega B97XD functional consider MO4 (M = Ru, Os) as the Lewis acid, paired with a series of pi electron donors C2H2, C2H4, C6H6, C4H5N, C4H4O, and C4H4S. The calculations establish interaction energies in the range between 9.5 and 26.4 kJ/mol. Os engages in stronger interactions than does Ru, and those involving more extensive pi-systems within the aromatic rings form stronger bonds than do the smaller ethylene and acetylene. Extensive analysis questions the existence of a true Osme bond, as the bonding chiefly involves interactions with the three O atoms of MO4 that lie closest to the pi-system, via pi(C-C)->sigma*(M-O) transfers. These interactions are supplemented by back donation from M-O bonds to the pi*(CC) antibonding orbitals of the pi-systems. Dispersion makes a large contribution to these interactions, higher than electrostatics and much greater than induction.