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相同相的催化剂。 然而，均相催化的困难涉及从催化剂中分离产物，使得催化剂可以再利用。 这种分离的困难导致环境成本和财务成本都很高。这个问题的一个潜在的解决方案涉及氟两相催化（FBC）。 这种催化方法需要在室温下不混合但在较高温度下联合收割机的两相;有机相含有反应物物质，而氟相含有催化剂。 加热使两相混合，并且反应在该单相中催化地发生。 在冷却时，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。因此，该方法的成功取决于催化剂的优先溶解性。 由于三芳基膦配体已被证明可用于如此多的催化方法中，因此迄今为止设计此类催化剂的努力已采用了这些连接有全氟烷基“马尾辫”的配体。然而，到目前为止，使用这样的配体尚未获得所需的溶解度性质。 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;随着这些化合物降解，它们变得生物累积和持久。 这可以使用不具有相同环境问题的氟化聚醚来解决，并且还具有更适合FBC的溶解度特性。这项研究计划的主要目标是双重的。 1)2）合成含氟聚醚的三芳基膦配体-CF_2CF（CF_3）[OCF_2CF（CF_3）]_nF;

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.