Extreme Oxatriquinanes: Structural Characterization of alpha-Oxyoxonium Species with Extraordinarily Long Carbon-Oxygen Bonds

Gunbas G., Sheppard W. L., Fettinger J. C., Olmstead M. M., MASCAL M.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol.135, no.22, pp.8173-8176, 2013 (SCI-Expanded) identifier identifier identifier

  • 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.