This research was supported by the NSF (Grants CHE-0431749 to R.W. and CHE-0345240 to R.A.M.) and Rutgers University. We thank Dr. Seho Kim for assistance with NMR spectroscopic experiments and Prof. Karsten Krogh-Jespersen for helpful suggestions.
Fluorophenoxycarbene inside a Hemicarcerand: A Bottled Singlet Carbene†
Article first published online: 21 FEB 2005
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 44, Issue 13, pages 1994–1997, March 18, 2005
How to Cite
Liu, X., Chu, G., Moss, R. A., Sauers, R. R. and Warmuth, R. (2005), Fluorophenoxycarbene inside a Hemicarcerand: A Bottled Singlet Carbene. Angew. Chem. Int. Ed., 44: 1994–1997. doi: 10.1002/anie.200462633
- Issue published online: 16 MAR 2005
- Article first published online: 21 FEB 2005
- Manuscript Received: 17 NOV 2004
- host–guest systems;
- NMR spectroscopy;
- reactive intermediates
Long live the carbene: Longevity is granted to fluorophenoxycarbene when it is generated photochemically from fluorophenoxydiazirine (see picture) inside a hemicarcerand. This fleeting, and otherwise nonisolable, singlet carbene is the first electron-deficient species that has been stabilized by trapping. NOE experiments suggest that the carbene adopts the intrinsically less stable cis conformation in the confined inner phase.