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

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，均相催化的困难包括将产物与催化剂分离，以便催化剂可以重复使用。这种分离困难导致高昂的成本，包括环境和财务成本。这个问题的一个潜在解决方案涉及氟两相催化(FBC)。这类催化过程需要两相，这两相在室温下不会混合，但在较高温度下结合；有机相包含反应物物种，而氟相包含催化剂。加热允许两相混合，反应在这一单一相中催化进行。冷却时，两相再次分离，一相包含催化剂，然后可重复使用，另一相包含反应产物。因此，这一过程的成功取决于催化剂的优先溶解性。由于三芳基膦配体在如此多的催化过程中被证明是有用的，到目前为止，设计这种催化剂的努力都使用了这些带有全氟烷基马尾辫的配体。然而，到目前为止，使用这种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，它们带来了环境挑战；随着这些化合物的降解，它们变成了生物累积和持久性的。这可以使用不具有相同环境问题的含氟聚醚来解决，并且也将具有更适合于FBC的溶解特性。本研究计划的主要目标有两个：(1)开发含氟聚醚的新型三芳基膦配体-CF2CF(CF3)[OCF2CF(CF3)]Nf；2)合成这些配体的Rh(I)配合物，并测试它们在氢甲酰化、氢化、Heck反应和聚合中的催化能力。

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.