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Etude théorique de la réactivité élémentaire du Bore atomique

Abstract : The organoborane chemistry is of great interest for chemists since more than one hundred years. On the other hand, the atomic boron chemistry is a quasi-virgin field of research. In the first part, we have participated to the identification of several bore-ethylene and bore-ethane reactions products isolated in argon matrix. Structures, energetic and vibrational properties for a number of BC2Hn (n = 3, 4, 5) species have been examined using ab initio and DFT methods. The comparison between the calculated IR spectra and the observed ones allowed to identify new small organoboranes. In second part, we have established the mechanisms for some boron reactions in order to better understand the boron atom reactivity. During the study of the B + H2O reaction, we have tested and validated a methodology for the determination of reaction mechanisms. This work combining ab initio and DFT calculations demonstrated the existence of an activation barrier for this reaction, in agreement with measured rate constant. Moreover, we proposed a mechanism for the previously unexplained formation of BO (A 2Pi) species. At last, the previous methodology was used to predict the mechanism of the bore-acetylene and bore-ethylene reactions. This study was led in same time as crossed beams experiments and allowed to identify unambiguously the products formed in this conditions: the HBCC molecule for the first reaction and the aromatic borirene molecule (c-HBC2H2) for the second one. These works have also showed that the two reactions could occur spontaneously if the boron atom adds initially to the pi CC bond. About the boreethylene reaction, the calculations exhibit several pathways able to compete with the borirene molecule formation.
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Submitted on : Friday, October 3, 2003 - 5:36:12 PM
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Nicolas Galland. Etude théorique de la réactivité élémentaire du Bore atomique. Autre. Université Sciences et Technologies - Bordeaux I, 2002. Français. ⟨tel-00003463⟩

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