Highly efficient and selective aqueous phase hydrogenation of aryl ketones, aldehydes, furfural and levulinic acid and its ethyl ester catalyzed by phosphine oxide-decorated polymer immobilized ionic liquid-stabilized ruthenium nanoparticles
Highly efficient and selective aqueous phase hydrogenation of aryl ketones, aldehydes, furfural and levulinic acid and its ethyl ester catalyzed by phosphine oxide-decorated polymer immobilized ionic liquid-stabilized ruthenium nanoparticles
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氧化膦修饰聚合物固定离子液体稳定钌纳米颗粒催化芳基酮、醛、糠醛和乙酰丙酸及其乙酯高效选择性水相加氢
DOI：
10.1039/d2cy00205a
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发表时间：
2022
影响因子：
5
通讯作者：
Doherty S
中科院分区：
文献类型：
--
作者：
Doherty S
将膦修饰的苯乙烯基聚合物固定化离子液体（PPh 2-PIIL）与钌（III）络合物浸渍导致钌的容易还原，得到Ru（II）浸渍的氧化膦修饰的PIIL（OPPh 2 PIIL）。衍生的氧化膦修饰的聚合物固定化离子液体稳定的RuNPs（RuNP@OPPh2-PIILS）催化高效和选择性的水相还原芳基和杂芳基酮和醛（包括糠醛）中的羰基，以及乙酰丙酸及其乙酯的氢化以提供γ-戊内酯（GVL）。虽然这是第一次报告的RuNP稳定的氧化膦改性的支持，似乎有几个最近的例子，类似的偶然氧化过程中的RuNP的合成，通过浸渍的膦修饰的聚合物与钌的氧化物;因为这些要么被误解或不承认这样，我们已经进行了详细的表征和评价这个系统。令人放心的是，由氧化膦修饰的聚合物固定化的离子液体（OPPh 2-PIIL）用钌浸渍的RuNP@OPPh2-PILs与直接由RuCl 3和PPh 2-PIIL制备的RuNP@OPPh2-PIIL一样有效。将PEG结合到聚合物载体中改善了催化剂性能，并且对于苯乙酮的水相氢化获得的2350 h-1的初始TOF是所报道的钌纳米颗粒基催化剂的最高TOF之一。在最佳条件下，RuNP@OPPh2-PEGPIILS循环10次，活性只有轻微降低，选择性没有可检测到的变化。对于CO在一系列取代的芳基和杂芳基酮上的氢化，也获得了高产率和优异的选择性。芳环和CO的完全氢化也可以通过相应地提高压力和温度来实现。相同的系统还催化糠醛在温和条件下的水相氢化，初始TOF为3160 h−1，以及乙酰丙酸及其乙酯选择性氢化为γ-戊内酯（GVL）;后者的反应时间可以通过添加丁酸或Amberlyst H-15而显著缩短。
Impregnation of phosphine-decorated styrene-based polymer immobilized ionic liquid (PPh2-PIIL) with ruthenium(III) trichloride resulted in facile reduction of the ruthenium to afford Ru(II)-impregnated phosphine oxide-decorated PIIL (OPPh2PIIL). The derived phosphine oxide-decorated polymer immobilized ionic liquid-stabilized RuNPs (RuNP@OPPh2-PIILS) catalyse the highly efficient and selective aqueous phase reduction of the carbonyl group in aryl and heteroaryl ketones and aldehydes, including furfural, as well as the hydrogenation of levulinic acid and its ethyl ester to afford γ-valerolactone (GVL). While this is the first report of RuNPs stabilized by a phosphine oxide-modified support, there appear to be several recent examples of similar serendipitous oxidations during the synthesis of RuNPs by impregnation of a phosphine-decorated polymer with ruthenium trichloride; as these were either misinterpreted or not recognised as such we have carried out a detailed characterization and evaluation of this system. Reassuringly, RuNP@OPPh2-PIILS generated from phosphine oxide-decorated polymer immobilized ionic liquid (OPPh2-PIIL) impregnated with ruthenium trichloride is as efficient as that prepared directly from RuCl3 and PPh2-PIIL. Incorporation of PEG into the polymer support improved catalyst performance and the initial TOF of 2350 h−1 obtained for the aqueous phase hydrogenation of acetophenone is among the highest to be reported for a ruthenium nanoparticle-based catalyst. Under optimum conditions, RuNP@OPPh2-PEGPIILS recycled ten times with only a minor reduction in activity and no detectable change in selectivity. High yields and excellent selectivities were also obtained for hydrogenation of the CO across a range of substituted aryl and heteroaryl ketones. Complete hydrogenation of the aromatic ring and CO could also be achieved by increasing the pressure and temperature accordingly. The same system also catalyzes the aqueous phase hydrogenation of furfural under mild conditions with an initial TOF of 3160 h−1 as well as the selective hydrogenation of levulinic acid and its ethyl ester to γ-valerolactone (GVL); reaction times for the latter could be reduced quite significantly by addition of either butyric acid or Amberlyst H-15.