Utilizing poly(hexafluoropropylene oxide) ligands in fluorous biphase catalysis (FBC)

在含氟双相催化 (FBC) 中使用聚（六氟环氧丙烷）配体

• 批准号: 261503-2006
• 负责人: Friesen, Chadron
• 金额: $ 1.46万
• 依托单位: Trinity Western University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Group
• 财政年份: 2006
• 资助国家: 加拿大
• 起止时间: 2006-01-01 至 2007-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=330635
• 关键词: Utilizing; poly; hexafluoropropylene; oxide; ligands

Many industrial processes employ homogeneous catalysts, catalysts that are in the same phase as the reactants and products.  However, a difficulty with homogeneous catalysis involves the separation of the products from the catalyst so that the catalyst can then be reused.  This difficulty in separation results in high costs, both environmental as well as financial. A potential solution to this problem involves fluorous biphase catalysis (FBC).  Such catalytic processes require two phases that do not blend at room temperature but combine at higher temperatures; an organic phase contains the reactant species, while a fluorous phase contains the catalyst.  Heating allows the two phases to blend and the reaction takes place catalytically in this single phase.  On cooling the two phases separate out again, with one containing the catalyst that can then be reused and the other phase containing the reaction products. The success of this process is therefore dependent upon the preferential solubility of the catalyst.  Since triaryl phosphine ligands have proved to be useful in so many catalytic processes, efforts to design such catalysts have thus far employed these ligands with a perfluoroalkyl "ponytail" attached. However, to this point the desired solubility properties have not yet been attained using such ligands.  A further problem with employing perfluoroalkyl ponytails is that they introduce environmental challenges; as these compounds degrade they become bio-accumulative and persistent.  This may be solved using fluorinated polyethers which do not possess the same environmental concerns, and will also have solubility properties more suited to FBC. The primary objectives of this research program are two-fold.  1) to develop new triarylphosphine ligands containing fluorinated polyethers, -CF2CF(CF3)[OCF2CF(CF3)]nF; 2) to synthesize Rh(I) complexes of these ligands and test their catalytic ability in hydroformylation, hydrogenation, Heck reactions, and polymerizations.

许多工业过程使用均相催化剂，即与反应物和产物处于同一相的催化剂。然而，均相催化的困难在于将产物与催化剂分离，以便催化剂可以重复使用。这种分离的困难导致环境和财务成本高。这一问题的一个潜在解决方案涉及氟两相催化（FBC）。这种催化过程需要在室温下不混合但在较高温度下联合收割机结合的两相;有机相含有反应物，而氟相含有催化剂。加热使两相混合，反应在这一单一相中进行催化。冷却时两相再次分离，其中一相含有可再利用的催化剂，另一相含有反应产物。由于三芳基膦配体已被证明可用于许多催化方法中，因此迄今为止，设计此类催化剂的努力都是使用这些连接有全氟烷基“马尾辫”的配体。然而，到目前为止，使用这些配体还没有达到所需的溶解性能。使用全氟烷基马尾辫的另一个问题是，它们会带来环境挑战;随着这些化合物的降解，它们会变得生物累积和持久。这可以通过使用氟化聚醚来解决，氟化聚醚不具有相同的环境问题，并且也具有更适合FBC的溶解性能。本研究计划的主要目的有两个：1）开发新的含氟聚醚的三芳基膦配体-CF_2CF（CF_3）[OCF_2CF（CF_3）]nF; 2）合成这些配体的Rh（I）配合物，并测试它们在加氢、氢化、Heck反应和聚合中的催化性能。