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Solvent-free oxidation of straight-chain aliphatic primary alcohols by polymer-grafted vanadium complexes
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2021-09-07 , DOI: 10.1002/aoc.6437 Payal Kachhap 1 , Nikita Chaudhary 1 , Chanchal Haldar 1
Applied Organometallic Chemistry ( IF 3.7 ) Pub Date : 2021-09-07 , DOI: 10.1002/aoc.6437 Payal Kachhap 1 , Nikita Chaudhary 1 , Chanchal Haldar 1
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Oxidovanadium(IV) complexes [VO(tertacac)2] (1), [VO(dipd)2] (2), and [VO(phbd)2] (3) were synthesized by reacting [VO(acac)2] with 2,2,6,6-tetramethyl-3,5-hepatanedione, 1,3-diphenyl-1,3-propanedione, and 1-phenyl-1,3-butanedione, respectively. Imidazole-modified Merrifield resin was used for the heterogenization of complexes 1–3. During the process of heterogenization, the V4+ center in complex 2 converts into V5+, whereas the other two complexes 1 and 3 remain in the oxidovanadium(IV) state in the polymer matrix. Theoretically, calculated IPA values of 1–3 suggest that 2 is prone to oxidation compared with 1 and 3, which was also supported by the absence of EPR lines in 5. Polymer-supported complexes Ps-Im-[VIVO(tertacac)2] (4), Ps-Im-[VVO2(dipd)2] (5), and Ps-Im-[VIVO(phbd)2] (6) were applied for the solvent-free heterogenous oxidation of a series of straight-chain aliphatic alcohols in the presence of H2O2 at 60°C and showed excellent substrate conversion specially for the alcohols with fewer carbon atoms. Higher reaction temperature improves the substrate conversion significantly for the alcohols containing more carbon atoms such as 1-pentanol, 1-hexanol, and 1-heptanol while using optimized reaction conditions. However, alcohols with fewer carbon atoms seem less affected by reaction temperatures higher than the optimized temperature. A decreasing trend in the selectivity(%) of carboxylic acid was observed with increasing carbon atoms among the examined alcohols, whereas the selectivity towards aldehydes increased. The order of efficiency of the supported catalysts is 4 > 6 > 5 in terms of turnover frequency (TOF) values and substrate conversion, further supported by theoretical calculations.
中文翻译：
聚合物接枝钒配合物无溶剂氧化直链脂肪族伯醇
氧化钒(IV)配合物[VO( tert acac) 2 ] ( 1 )、[VO(dipd) 2 ] ( 2 )和[VO(phbd) 2 ] ( 3 )是通过[VO(acac) 2 ]反应合成的分别为 2,2,6,6-四甲基-3,5-庚二酮、1,3-二苯基-1,3-丙二酮和 1-苯基-1,3-丁二酮。咪唑改性的 Merrifield 树脂用于复合物1-3的异质化。在异质化过程中，配合物2中的V 4+中心转化为V 5+，而另外两个配合物1和3在聚合物基质中保持氧化钒 (IV) 状态。从理论上讲，计算出的 IP A值为1-3表明2与1和3相比更容易氧化，这也得到了5 中缺乏 EPR 线的支持。聚合物负载的复合物 Ps-Im-[V IV O( tert acac) 2 ] ( 4 )、Ps-Im-[V V O 2 (dipd) 2 ] ( 5 ) 和 Ps-Im-[V IV O( phbd) 2 ] ( 6) 用于在 H 2 O 2存在下对一系列直链脂肪醇进行无溶剂多相氧化在 60°C 下表现出优异的底物转化率，特别是对于碳原子较少的醇。对于含更多碳原子的醇，如 1-戊醇、1-己醇和 1-庚醇，在优化反应条件的同时，较高的反应温度显着提高了底物转化率。然而，具有较少碳原子的醇似乎受高于优化温度的反应温度的影响较小。随着被测醇中碳原子的增加，观察到羧酸的选择性（％）呈下降趋势，而对醛的选择性增加。负载型催化剂的效率顺序为4 > 6 > 5 在周转频率 (TOF) 值和底物转化率方面，理论计算进一步支持。
更新日期：2021-09-07
中文翻译：
聚合物接枝钒配合物无溶剂氧化直链脂肪族伯醇
氧化钒(IV)配合物[VO( tert acac) 2 ] ( 1 )、[VO(dipd) 2 ] ( 2 )和[VO(phbd) 2 ] ( 3 )是通过[VO(acac) 2 ]反应合成的分别为 2,2,6,6-四甲基-3,5-庚二酮、1,3-二苯基-1,3-丙二酮和 1-苯基-1,3-丁二酮。咪唑改性的 Merrifield 树脂用于复合物1-3的异质化。在异质化过程中，配合物2中的V 4+中心转化为V 5+，而另外两个配合物1和3在聚合物基质中保持氧化钒 (IV) 状态。从理论上讲，计算出的 IP A值为1-3表明2与1和3相比更容易氧化，这也得到了5 中缺乏 EPR 线的支持。聚合物负载的复合物 Ps-Im-[V IV O( tert acac) 2 ] ( 4 )、Ps-Im-[V V O 2 (dipd) 2 ] ( 5 ) 和 Ps-Im-[V IV O( phbd) 2 ] ( 6) 用于在 H 2 O 2存在下对一系列直链脂肪醇进行无溶剂多相氧化在 60°C 下表现出优异的底物转化率，特别是对于碳原子较少的醇。对于含更多碳原子的醇，如 1-戊醇、1-己醇和 1-庚醇，在优化反应条件的同时，较高的反应温度显着提高了底物转化率。然而，具有较少碳原子的醇似乎受高于优化温度的反应温度的影响较小。随着被测醇中碳原子的增加，观察到羧酸的选择性（％）呈下降趋势，而对醛的选择性增加。负载型催化剂的效率顺序为4 > 6 > 5 在周转频率 (TOF) 值和底物转化率方面，理论计算进一步支持。
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