Teddy Butscher

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules – glycolaldehyde, ethylene glycol, and polyoxymethylene – through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H 2 CO proceed preferentially through CH 2 OH intermediate radicals rather than the CH 3 O radical.

Intramolecular Hydrogen Bond in Alkoxyamines. Influence on the C–ON Bond Homolysis

The C-ON bond homolysis in alkoxyamines can be influenced by the presence of an intramolecular hydrogen bond (IHB) between the alkyl and the nitroxyl fragments, which leads to an 8-fold decrease in the homolysis rate constant k(d). When the IHB is disrupted by the solvent or by substitution of the hydrogen involved in the IHB by a protecting group (OMe, OAc, OBz, OBn, or OTBDMS), a higher homolysis rate constant k(d) is observed, as expected from the correlations developed by Marque (Bertin, D.; Gigmes, D.; Marque, S.; Tordo, P. Macromolecules 2005, 38, 2638-2650). Results were confirmed by DFT calculations at the B3LYP/6-31G(d,p) level.

β-Phosphorus hyperfine coupling constant in nitroxides: 5. Solvent effect

Recently, we published the titration of water in organic solvents and conversely using this family of nitroxides (Org. Biomol. Chem. 2015 ASAP). In this article, we show that the aβ,P of persistent cyclic β-phosphorylated nitroxides decreases with the normalized polarity Reichardts constant ENT. Koppel–Palm and Kalmet–Abboud–Taft relationships were applied to get a deeper insight into the effects influencing aN and aβ,P: polarity/polarizability, hydrogen bond donor property, and structuredness of the cybotactic region.

Solvent effect in β-phosphorylated nitroxides. Part 4: detection of traces of water by electron paramagnetic resonance.

For decades, the nitrogene hyperfine coupling constant aN of nitroxides has been applied to probe their environment using EPR. However, the small changes observed (≈2 G from n-pentane to water) with the solvent polarity allow only a qualitative discussion. A stable β-phosphorylated nitroxide exhibiting a small change in aN (≈3 G from n-pentane to water) and a striking change (≈25 G from n-pentane to water) in phosphorus hyperfine coupling constant aP with the polarity of solvent was prepared and used to develop the first procedure for the titration of water in THF by EPR, down to 0.1% v/v.

Intramolecular Hydrogen Bond Reverting the Solvent Effect on Phosphorus Hyperfine Coupling Constants of β-Phosphorylated Nitroxides

Recently, we reported a dramatic solvent effect on the phosphorus hyperfine coupling constant aP of β-phosphorylated six-membered ring nitroxides, that is, approximately 25 G of difference in aP from n-hexane to water (Org. Biomol. Chem. 2016, 14, -1228-1292). In this article, we report on the effect of intramolecular hydrogen bonding (IHB) in three nitroxides exhibiting IHB between the hydroxyl and diethylphosphoryl groups and one exhibiting IHB between the hydroxyl group and the nitroxyl moiety. It is observed that for the first three nitroxides, aP increases with increasing polarity/polarizability and hydrogen bond donor (HBD) properties of the solvent (π* and α, respectively)-in sharp contrast to the data reported in the literature-and for the last nitroxide, aP decreases with π* and α. In fact, the occurrence of IHB induces a large strain, its suppression by hydrogen bond acceptor (HBA) solvents affords an increase in aP .