Extreme Oxatriquinanes: Structural Characterization of alpha-Oxyoxonium Species with Extraordinarily Long Carbon-Oxygen Bonds
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol.135, no.22, pp.8173-8176, 2013 (SCI-Expanded, Scopus)
- Publication Type: Article / Article
- Volume: 135 Issue: 22
- Publication Date: 2013
- Doi Number: 10.1021/ja4032715
- Journal Name: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Page Numbers: pp.8173-8176
- Middle East Technical University Affiliated: Yes
Abstract
The first stable alpha-oxyoxonium species have been synthesized and characterized. Strong donation of nonbonding electrons on oxygen into the adjacent sigma*(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 alpha-hydroxy and alpha-methoxy oxatriquinane triflates reveals 1.658 and 1.619 angstrom C-O+ bond lengths, respectively, the former of which is a new record for the C-O bond.