Energy analysis of metal–metal bonding in [RM–MR] (M = Zn, Cd, Hg; R = CH3, SiH3, GeH3, C5H5, C5Me5)

Abstract The metal–metal bonds of the title compounds have been investigated with the help of energy decomposition analysis at the DFT/TZ2P level. In good agreement with experiment, computations yield Hg–Hg bond distance in [H3SiHg–HgSiH3] of 2.706 A and Zn–Zn bond distance in [(η5-C5Me5)Zn–Zn(η5-C5Me5)] of 2.281 A. The Cd–Cd bond distances are longer than the Hg–Hg bond distances. Bond dissociation energies (-BDE) for Zn–Zn bonds in zincocene −70.6 kcal/mol in [(η5-C5H5)2Zn2] and −70.3 kcal/mol in [(η5-C5Me5)2Zn2] are greater amongst the compounds under study. In addition, [(η5-C5H5)2M2] is found to have a binding energy slightly larger than those in [(η5-C5Me5)2M2]. The trend of the M–M bond dissociation energy for the substituents R shows for metals the order GeH3

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