C2P2, team COMS (CNRS-UMR 5265), Université Lyon 1, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, 69626 Villeurbanne Cedex, France.
Chem Soc Rev. 2013 Dec 7;42(23):9035-54. doi: 10.1039/c3cs60115c. Epub 2013 Aug 14.
Olefin metathesis is increasingly incorporated in polyfunctional industrial processes. The classical WO3/SiO2 olefin metathesis catalyst is combined to other catalysts in order to afford higher added-value chemicals. However, the combination of several reactions, not only in a single reactor, but also stemming from a single, multifunctional surface species is a desirable improvement regarding process issues. Well-defined surface organometallic tungsten species can be designed to implement targeted functionalities (carbene, hydride, alkyl, …). By tuning the metal's coordination sphere, it is possible to combine metathesis with several reactions, such as (de)hydrogenation, dimerization or isomerization. Novel, unconventional reactions for the production and upgrading of alkanes and alkenes have thus been uncovered. The reactivity of this library of supported catalysts is discussed based on the type of mediated transformations: monofunctional (alkene and alkyne metathesis), bifunctional (1-butene or 2-butenes to propylene), trifunctional (ethylene to propylene, alkane metathesis, …). Mechanistic considerations will be discussed to put these results in a wider perspective for future developments.
烯烃复分解反应在多功能工业过程中得到了越来越多的应用。经典的 WO3/SiO2 烯烃复分解催化剂与其他催化剂结合，以提供更高附加值的化学品。然而，将多个反应组合在一起，不仅在单个反应器中，而且还源自单个多功能表面物种，是一个在工艺问题方面的理想改进。可以设计出明确的表面有机金属钨物种来实现靶向功能（卡宾、氢化物、烷基等）。通过调整金属的配位球，可以将复分解反应与其他反应（如（脱氢）、二聚化或异构化）结合起来。因此，已经发现了用于烷烃和烯烃生产和升级的新型非常规反应。根据介导转化的类型，讨论了该系列负载催化剂的反应性：单功能（烯烃和炔烃复分解）、双功能（1-丁烯或 2-丁烯到丙烯）、三功能（乙烯到丙烯、烷烃复分解等）。将讨论这些结果的机理考虑，以更广泛的视角来看待未来的发展。
