title: Nonpolar dihydrogen bonds--on a gliding scale from weak dihydrogen interaction to covalent H-H in symmetric radical cations [HnE-H-H-EHn]+.
abstract: The electronic structures and bonding patterns for a new class of radical cations, [HnE-H-H-EHn]+ (EHn=element hydride, E=element of Groups 15-18), have been investigated by applying quantum-chemical methods. All structures investigated give rise to symmetric potential energy minimum structures. We envisage clear periodic trends. The H--H bond length is shorter for elements toward the bottom of the periodic table of elements, and a short H--H bond corresponds to accumulation of electron density in the central H--H region. All [HnE-H-H-EHn]+ of Groups 15-17 are thermodynamically unstable towards loss of either H2 or H. The barriers for these dissociations are rather low. The Group 18 congeners, except E=Xe, appear to be global minima of the respective potential energy surfaces. The findings are discussed in terms of H2 bond activation, and a general mechanistic scheme for the standard reduction process 2H+ + 2e(-) --> H2 is given. Finally, it is proposed that some of the symmetric radical cations are likely to be observed in mass spectrometric or matrix isolation experiments.
authors.affiliation: Fachbereich Chemie, Phillipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Krapp
authors.forename: Gernot
authors.initials: G
authors.lastname: Frenking
authors.forename: Einar
authors.initials: E
authors.lastname: Uggerud