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Dihydrogen Activation at Non-Metallic Centers (DANMC)
Dihydrogen Activation at Non-Metallic Centers
(DANMC)
Date du début: 1 avr. 2010,
Date de fin: 31 juil. 2011
PROJET
TERMINÉ
"Molecular hydrogen is widely used today in chemical reactions, such as the addition of H2 to organic molecules, a process referred to as hydrogenation. These transformations are among the largest-volume industrial processes: for example, crude oil is treated with H2, and 108 tons of ammonia-based fertilizers are produced each year via catalytic hydrogenation. Also, hydrogen is arguably one of the most promising and valuable future fuels. Thus, any improvement in catalyst efficiency, cost efficiency, or availability would help to cut the cost of these important processes, and advances made in the field have a deep impact on both industrial and academic scenarios. Hydrogenations generally require a first step in which the strong H-H bond is cleaved. This splitting usually requires the action of a metal center, and both the mechanism and applications of transition metal catalyzed hydrogenations have been the subject of numerous studies.However, currently there is a growing interest to part from expensive and toxic transition metal catalysts, and redirect research towards more environmentally benign organic compounds. Recent studies have demonstrated the viability of this proposal. In 2006, a groundbreaking contribution described the metal-free activation of hydrogen. This new system, based on phosphinoboranes, can add H2 reversibly under mild conditions and functions as a catalyst for the hydrogenation of imines. Although the catalytic efficiency and scope are still very limited, these results indicate that it might be possible to develop practically useful systems for H2 activation based on organic compounds. The goal of our studies is to develop an efficient new system for heterolytic dihydrogen activation which contains boron as a hydride acceptor and oxygen as proton acceptor. Ideally, this process will be catalytic, and will be coupled with the reduction of an organic compound. Moreover, non-metallic catalysts could open ways to unusual reactivity and selectivity."
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