title: Extreme oxatriquinanes: structural characterization of α-oxyoxonium species with extraordinarily long carbon-oxygen bonds.
abstract: The first stable α-oxyoxonium species have been synthesized and characterized. Strong donation of nonbonding electrons on oxygen into the adjacent σ*(C-O(+)) orbital was predicted by modeling to result in unheard of carbon-oxygen bond lengths. The kinetic stability of the triquinane ring system provides a platform upon which to study these otherwise elusive species, which are evocative of intermediates on the acetalization reaction pathway. Crystallographic analysis of the α-hydroxy and α-methoxy oxatriquinane triflates reveals 1.658 and 1.619 Å C-O(+) bond lengths, respectively, the former of which is a new record for the C-O bond.
authors.affiliation: Department of Chemistry, University of California-Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Gorkem
authors.initials: G
authors.lastname: Gunbas
authors.forename: William L
authors.initials: WL
authors.lastname: Sheppard
authors.forename: James C
authors.initials: JC
authors.lastname: Fettinger
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.forename: Mark
authors.initials: M
authors.lastname: Mascal