title: Alkyl radicals as hydrogen bond acceptors: computational evidence.
abstract: Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better acceptors than formaldehyde molecules, while propyl radicals are as good as H(2)O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting that the charge-transfer aspects of hydrogen bonding are particularly conspicuous when the acceptor polarity and basicity is low.
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark.
authors.forename: Steen
authors.initials: S
authors.lastname: Hammerum
mesh_terms: D000473:Alkanes / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D013055:Spectrophotometry, Infrared; D055672:Static Electricity; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D000473:Alkanes; D005609:Free Radicals; D014867:Water