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Reactive small species

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Synthesis of compounds related to astrochemistry

Synthesis of cyanopolyynes

Cyanopolyynes, the formula of which is H-(C☰C)n-CN, are probably the most interesting organic compounds detected so far in the interstellar medium. However, their synthesis in the laboratory is very challenging because of their instability, and even though the first member of the family, the cyanoacetylene (n=1), has been synthesized in 1910, our group was the first to synthesize the next member of the family, the cyanobutadiyne (n = 2) [1]. Its reactivity has thus been investigated, as well as some mechanisms that could lead to this compound in the interstellar medium or the atmosphere of Titan. The methylated counterpart H3C-(C☰C)2-CN has also been investigated in the context of space science. [2]

In order to synthesize the following members of this family, we synthesized the bromocyanobutadiyne (Br-C☰C-C☰C-CN) and reacted it with terminal acetylenes. Contrary to what was anticipated, the corresponding cyanopolyynes were not obtained but other complex molecules were isolated, following an unprecedented mechanism [3].

Isocyanides, nitriles, aldehydes, … as candidates for the interstellar medium

We are also interested in helping the astrophysicists to detect new organic compounds in the interstellar medium. To achieve this goal, we suggest and synthesize relevant organic compounds. Thus, the microwave spectra of these compounds are recorded in collaboration with other groups in order to identify them in space [4]. Are particularly studied cyanides, isocyanides, isocyanates and isomers [5]. The main goal of this study is to improve the understanding of the chemistry of these media to be able to predict which other compounds are present.

Synthesis of complexes

Borane and alane complexes of amines, nitriles and phosphines have been synthesized and studied by spectroscopy. The potential application of some of them for hydrogen storage has been investigated [6]. Moreover, some of them could be precursors of free functionalized boranes.

Reactivity of ynamides with tetracyanoethylene

We recently studied the sequence of [2+2]cycloaddition-retroelectrocyclisation between ynamides and tetracyanoethylene [7]. Actually, we carried out a methodology showing that it was possible to obtain 1,1,4,4-tetracyanobutadienes from several ynamides and tetracyanoethylene by simply mixing them together in dichloromethane at room temperature. This reaction is very tolerant to numerous substituents. We are currently investigating the possibility to extend this methodology to more complex systems and to study their properties in non-linear optics [8].

Staff : Jean-Claude Guillemin, Yann Trolez

[1Y. Trolez, J.-C. Guillemin, Angew. Chem. Int. Ed. 2005, 44, 7224-7226.

[2a) N. Kerisit, L. Toupet, Y. Trolez, J.-C. Guillemin, Chem. Eur. J. 2013, 19, 17683-17686; b) N. Kerisit, C. Rouxel, S. Colombel-Rouen, L. Toupet, J.-C. Guillemin, Y. Trolez, J. Org. Chem. 2016, 81, 3560-3567.

[3N. Kerisit, L. Toupet, P. Larini, L. Perrin, J.-C. Guillemin, Y. Trolez, Chem. Eur. J. 2015, 21, 6042-6047.

[4J. Cernicharo, Z. Kisiel, B. Tercero, L. Kolesniková, I. R. Medvedev, A. López, S. Fortman, M. Winnewisser, F. C. de Lucia, J. L. Alonso, J.-C. Guillemin, A&A, 2016, 587, L4.

[5a) H. Møllendal, S. Samdal, A. Matrane, J.-C. Guillemin, J. Phys. Chem. A, 2011, 115, 7978–7983; b) A. Chrostowska, C. Darrigan, A. Dargelos, A. Benidar, J.-C. Guillemin, ChemPhysChem 2015, 16, 3660 –3671.

[6B. Nemeth, J.-P. Guegan, T. Veszpremi, J.-C. Guillemin, Inorg. Chem. 2013, 52, 346-354.

[7M. Betou, N. Kerisit, E. Meledje, Y. R. Leroux, C. Katan, J.-F. Halet, J.-C. Guillemin, Y. Trolez Chem. Eur. J. 2014, 20, 9553-9557.

[8Z. Pokladek, N. Ripoche, M. Betou, Y. Trolez, O. Mongin, J. Olesiak-Banska, K. Matczyszyn, M. Samoc, M. G. Humphrey, M. Blanchard-Desce, F. Paul, Chem. Eur. J. 2016, 22, 10155-10167.