Redox‐Triggered Reversible Interconversion of a Monocyclic and a Bicyclic Phosphorus Heterocycle1. (19th May 2014)

• Record Type: Journal Article
• Authors: Heift, Dominikus; Benkő, Zoltán; Grützmacher, Hansjörg
• Is Part Of: Angewandte Chemie. Volume 126:Number 26(2014)
• Page Start: 6875
• Page End: 6879
• Publication Date: 2014-05-19
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201402884
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 [<bold>3 a</bold>]⁻. The oxidation of this anion with elemental iodine causes an intramolecular rearrangement reaction to give a bicyclic 1, 3, 2‐diazaphospholenium cation [<bold>6</bold>]⁺. This umpolung of electronic properties from non‐aromatic to highly aromatic is reversible, and the cation [<bold>6</bold>]^{<bold>+</bold>} is reduced with elemental magnesium to reform the 1, 3, 5‐diazaphosphinanide anion [<bold>3 a</bold>]⁻. Theoretical calculations suggest that phosphinidene species are involved in the rearrangement processes.</p> </abstract>