title: Host-guest hydrogen atom transfer induced by electron capture.
abstract: 1,n-Alkanediammonium cations in noncovalent complexes with two dibenzo-18-crown-6-ether (DBCE) ligands undergo an unusual intramolecular tandem hydrogen atom and proton transfer to the crown ether ligand upon charge reduction by electron capture. Deuterium labeling established that both migrating hydrogens originated from the ammonium groups. The double hydrogen transfer was found to depend on the length of the alkane chain connecting the ammonium groups. Ab initio calculations provided structures for select alkanediammonium.dibenzo-18-crown-6-ether complexes and dissociation products. This first observation of an intra-complex hydrogen transfer is explained by the unusual electronic properties of the complexes and the substantial hydrogen atom affinity of the aromatic rings in the crown ligand.
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington, USA.
authors.forename: Changtong
authors.initials: C
authors.lastname: Hao
authors.forename: Frantisek
authors.initials: F
authors.lastname: Turecek