Structure and fragmentation of Ag2H+ and Ag2CH3+ (original) (raw)

1987, Inorganic Chemistry

Hartree-Fock-Slater calculations were completed on the title ions. Both of these three-center two-electron bond systems are calculated to be triangular with the proton or the methyl group bridging a lengthened (-0.1 A) Ag, bond. The proton affinity of Ag2 is calculated to be 193.5 kcal/mol and the methyl cation affinity is 128.7 kcal/mol. A bond energy decomposition analysis reveals that the lower methyl cation affinity results from the larger steric interaction of the methyl cation with the Ag, fragment and from the energy required to make the methyl cation pyramidal in order to prepare it for bonding to the Ag, fragment. The fragmentation energies of the ions are calculated, and the results are discussed with respect to the collision-induced-dissociation work of Busch et al. 1984, 23, 4093. DeKock, R. L.; Dutler, R.; Rauk, R.; van Zee, R. D. Inorg. Chem. 1986, 25, 3329. DeKock, R. L.; Bosma, W. B., submitted for publication in J. Chem. Educ. Bau, R.; Teller, R. G.; Kirtley, S. W.; Koetzle, T. F. Acc. Chem. Res. 1979.12, 176. Shore, S. G.; Lawrence, S. H.; Watkins, M. I.; Bau, R.