Publication details for Dr Dominikus HeiftHeift, D., Benkő, Z. & Grützmacher, H. (2014). Redox-triggered reversible interconversion of a monocyclic and a bicyclic phosphorus heterocycle. Angewandte Chemie International Edition 53(26): 6757-6761.
- Publication type: Journal Article
- ISSN/ISBN: 1433-7851, 1521-3773
- DOI: 10.1002/anie.201402884
- Further publication details on publisher web site
Author(s) from Durham
Molecules which change their structures significantly and reversibly upon an oxidation or reduction process have potential as future components of smart materials. A prerequisite for such an application is that the molecules should undergo the redox-coupled transformation within a reasonable electrochemical window and lock into stable redox states. Sodium phosphaethynolate reacts with two equivalents of dicyclohexylcarbodiimide (DCC) to yield an anionic, imino-functionalized 1,3,5-diazaphosphinane [3 a]−. The oxidation of this anion with elemental iodine causes an intramolecular rearrangement reaction to give a bicyclic 1,3,2-diazaphospholenium cation +. This umpolung of electronic properties from non-aromatic to highly aromatic is reversible, and the cation + is reduced with elemental magnesium to reform the 1,3,5-diazaphosphinanide anion [3 a]−. Theoretical calculations suggest that phosphinidene species are involved in the rearrangement processes.