Amino-Modified Polymer Immobilized Ionic Liquid Stabilized Ruthenium Nanoparticles: Efficient and Selective Catalysts for the Partial and Complete Reduction of Quinolines
Amino-Modified Polymer Immobilized Ionic Liquid Stabilized Ruthenium Nanoparticles: Efficient and Selective Catalysts for the Partial and Complete Reduction of Quinolines
复制标题
氨基改性聚合物固定离子液体稳定钌纳米粒子：用于部分和完全还原喹啉的高效选择性催化剂
DOI：
10.1002/cctc.202300418
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发表时间：
2023
期刊：
影响因子：
4.5
通讯作者：
Alharbi A
中科院分区：
文献类型：
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作者：
Alharbi A
由氨基修饰的咪唑鎓基聚合物固定化离子液体稳定的RuNP催化二甲胺硼烷介导的喹啉还原为1，2-二氢喹啉（DHQ）和1，2，3，4-四氢喹啉（THQ）。在温和的条件下，在甲苯中以100%的选择性实现了3-取代喹啉部分还原为相应的1，2-二氢喹啉。这是第一个报告的选择性部分还原3-取代喹啉相应的1，2-二氢喹啉与非均相纳米粒子为基础的催化剂。通过调节反应时间，以高的选择性和良好的产率将多种取代喹啉还原为相应的1，2，3，4-四氢喹啉。1，2-二氢喹啉在甲苯中在60 °C下在不存在催化剂的情况下容易释放二氢，没有证据表明会发生氢化，因此是潜在的有机氢化物试剂。对于基于金属纳米颗粒的催化剂，用于还原喹啉的610摩尔喹啉转化摩尔Ru-1h-1的初始TOF是所报道的最高的，并且在65 °C下4小时后获得的96%的转化率显著高于其铂纳米颗粒对应物PtNP@NH2-PEGPIILS以及5重量/% Ru/C，其同时分别仅达到9%和11%的转化率。 热过滤实验表明，活性物种是异质的。
RuNPs stabilised by amino‐decorated imidazolium‐based polymer immobilized ionic liquids catalyse the dimethylamine borane mediated reduction of quinolines to 1,2‐dihydroquinoline (DHQ) and 1,2,3,4‐tetrahydroquinoline (THQ). Partial reduction of 3‐substituted quinolines to the corresponding 1,2‐dihydroquinoline was achieved with 100 % selectivity in toluene under mild conditions. This is the first report of the selective partial reduction of 3‐substituted quinolines to the corresponding 1,2‐dihydroquinolines with a heterogeneous nanoparticle‐based catalyst. A wide range of substituted quinolines have also been reduced to the corresponding 1,2,3,4‐tetrahydroquinoline with high selectivity and good yields by adjusting the reaction time. The 1,2‐dihydroquinolines readily release dihydrogen in toluene at 60 °C in the absence of catalyst with no evidence for disproportionation and as such are potential organo‐hydride reagents. The initial TOF of 610 mol quinoline converted mol Ru−1h−1for the reduction of quinoline is among the highest to be reported for a metal nanoparticle‐based catalyst and the conversion of 96 % obtained after 4 h at 65 °C is significantly higher than its platinum nanoparticle counterpart PtNP@NH2‐PEGPIILS as well as 5 wt/% Ru/C, which only reached 9 % and 11 % conversion, respectively, at the same time. Hot filtration experiments showed that the active species was heterogeneous.