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Redox‐Triggered Reversible Interconversion of a Monocyclic and a Bicyclic Phosphorus Heterocycle
Author(s) -
Heift Dominikus,
Benkő Zoltán,
Grützmacher Hansjörg
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402884
Subject(s) - umpolung , chemistry , redox , bicyclic molecule , intramolecular force , phosphinidene , molecule , electrochemistry , photochemistry , combinatorial chemistry , ion , inorganic chemistry , medicinal chemistry , organic chemistry , catalysis , electrode , nucleophile
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.