Redox-triggered reversible interconversion of a monocyclic and a bicyclic phosphorus heterocycle

Heift, D.; Benkő, Z.; Grützmacher, H.

Abstract

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 [6]+. This umpolung of electronic properties from non-aromatic to highly aromatic is reversible, and the cation [6]+ 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.

Citation

Heift, 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. https://doi.org/10.1002/anie.201402884

• Journal Article Type: Article
• Online Publication Date: May 19, 2014
• Publication Date: 2014-06
• Deposit Date: Feb 22, 2017
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 53
• Issue: 26
• Pages: 6757-6761
• DOI: https://doi.org/10.1002/anie.201402884
• Public URL: https://durham-repository.worktribe.com/output/1364136