Issue 7, 2013
From the journal:

New Journal of Chemistry

Diferrocenylpyrylium salts and electron rich bispyran from oxidative coupling of ferrocenylpyran. Example of redox systems switched by proton transfer†

Fatou Ba,a   Nolwenn Cabon,a   Pascal Le Poul,a   Samia Kahlal,b   Jean-Yves Saillard,b   Nicolas Le Poul,c   Stéphane Golhen,b   Bertrand Caro*a  and  Françoise Robin-Le Guena  

* Corresponding authors

a Institut des Sciences Chimiques de Rennes, U.M.R. CNRS 6226, I.U.T. Lannion, B.P. 30219, rue E. Branly 22302 Lannion, France
E-mail: bertrand.caro@univ-rennes1.fr
Fax: +33 (0)2 96 46 93 54
Tel: +33 (0)2 96 46 93 48

b Institut des Sciences Chimiques de Rennes, U.M.R. CNRS 6226, Université de Rennes 1, 263 avenue du Général Leclerc CS 74205 35042 Rennes Cedex, France

c Laboratoire de Chimie, Electrochimie Moléculaires et Chimie Analytique, U.M.R. CNRS 6521, Université de Bretagne Occidentale, 6 avenue Victor Le Gorgeu CS 93837 29238 Brest Cedex 3, France

Abstract

Electro or chemical oxidation of ferrocenylmethylenepyran gave an ethanediferrocenylbispyrylium salt through the dimerization of a ferrocenylpyran radical-cation (C–C bond making). Electro or chemical reduction gave back the ferrocenylmethylenepyran (C–C bond breaking). This electrochemical reverse system constitutes an example of C–C bond making–breaking process in a metallocenyl series with rather high stability. DFT calculations and electrochemical studies were carried out in order to determine the electronic structure of the radical cation intermediate, the role of the ferrocenyl groups and the mechanism of the C–C bond making and C–C bond breaking processes. Reversible deprotonation of the ethanediferrocenylbispyrylium salt afforded an extended diferrocenylbismethylenepyran, which was subsequently reversibly oxidized to an ethenediferrocenylbispyrylium salt. X-Ray crystallographic data of diferrocenylbismethylenepyran and ethenediferrocenylbispyrylium salt allowed to determine the molecular movements, which come with the electron transfer (ET). A comparison with the behavior of the corresponding isoelectronic bisdithiafulvenes (extended TTF) and bisdithiolium salts was made.

Graphical abstract: Diferrocenylpyrylium salts and electron rich bispyran from oxidative coupling of ferrocenylpyran. Example of redox systems switched by proton transfer

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Article information

DOI
https://doi.org/10.1039/C3NJ41126E
Article type
Paper
Submitted
12 Dec 2012
Accepted
28 Mar 2013
First published
02 Apr 2013

New J. Chem., 2013,37, 2066-2081

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Diferrocenylpyrylium salts and electron rich bispyran from oxidative coupling of ferrocenylpyran. Example of redox systems switched by proton transfer

F. Ba, N. Cabon, P. Le Poul, S. Kahlal, J. Saillard, N. Le Poul, S. Golhen, B. Caro and F. Robin-Le Guen, New J. Chem., 2013, 37, 2066 DOI: 10.1039/C3NJ41126E

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