Catalytic Oxidation of Aliphatic Alcohols by Graphene Oxide Supported Binuclear Dioxidovanadium (V) Complexes

IF 3 3区化学 Q2 CHEMISTRY, APPLIED Topics in Catalysis Pub Date : 2023-10-26 DOI:10.1007/s11244-023-01873-w

Payal Kachhap, Nikita Chaudhary, Chanchal Haldar

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Abstract

Two new oxidovanadium(IV) complexes [CH₂{V^IVO(sal-sc)}₂]·SO₄ (1) and [CH₂{V^IVO(sal-tc)}₂]·SO₄ (2) and dioxidovanadium(V) complexes K₂[CH₂{V^VO₂(sal-sc)}₂] (3) and K₂[CH₂{V^VO₂(sal-tc)}₂] (4) were synthesised. Thoroughly characterized dioxidovanadium(V) complexes 3 and 4 were covalently grafted on the nano-surface of graphene oxide and heterogeneous catalysts GO-[CH₂{V^VO₂(sal-sc)}₂] (5) and GO-[CH₂{V^VO₂(sal-tc)}₂] (6) were isolated. Both the supported catalysts 5–6 efficiently catalyzed a series of straight-chain primary aliphatic alcohols and cyclic secondary aliphatic alcohols in the presence of H₂O₂ without any additional solvent. Straight-chain primary alcohols show better reactivity than cyclic secondary alcohols. Moreover, the alcohols with fewer carbon atoms are more reactive, and reactivity decreases with increasing carbon chain length of the alcohols. With 96% and 92% substrate conversion in the presence of 5 and 6, respectively, ethanol showing the highest reactivity among the examined alcohols. All the listed primary aliphatic alcohols exhibit more than 65% substrate conversion. Irrespective of the substrate 5 shows better performance than 6. The catalytic reaction proceeds through a radical mechanism wherein the in situ generated reactive species CH₂{V^VO(O)₂(sal-sc)}₂].MeOH detected through HR-MS analysis is believed to be the active component responsible for the oxidation of the alcohols.

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氧化石墨烯负载的双核二氧化钒(V)配合物催化氧化脂肪族醇

合成了两个新的氧化钒（IV）配合物[CH2{VIVO(sal-sc)}2]·SO4(1)和[CH2{VIVO(sal-tc)}2]·SO4(2)和二氧化钒(V)配合物K2[CH2{VVO2(sal-sc)}2](3)和K2[CH2{VVO2(sal-tc)}2](4)。将二氧化钒(V)配合物3和4共价接枝在氧化石墨烯纳米表面，分离出了GO-[CH2{VVO2(sal-sc)}2](5)和GO-[CH2{VVO2(sal-tc)}2](6)两种非均相催化剂。负载型催化剂5 ~ 6在H2O2存在下均能高效催化一系列直链伯脂肪醇和环仲脂肪醇，无需添加任何溶剂。直链伯醇表现出比环仲醇更好的反应性。碳原子越少的醇反应性越强，反应性随碳链长度的增加而降低。在5和6的存在下，乙醇的底物转化率分别为96%和92%，在所检测的醇中表现出最高的反应活性。所有列出的伯脂肪族醇均表现出65%以上的底物转化率。无论基材是什么，5都比6表现出更好的性能。催化反应通过自由基机制进行，其中原位生成的反应物质CH2{VVO(O)2(sal-sc)}2]。通过HR-MS分析检测到的MeOH被认为是负责醇氧化的活性成分。图形抽象

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来源期刊

Topics in Catalysis 化学-物理化学

CiteScore

5.70

自引率

5.60%

发文量

197

审稿时长

2 months

期刊介绍： Topics in Catalysis publishes topical collections in all fields of catalysis which are composed only of invited articles from leading authors. The journal documents today’s emerging and critical trends in all branches of catalysis. Each themed issue is organized by renowned Guest Editors in collaboration with the Editors-in-Chief. Proposals for new topics are welcome and should be submitted directly to the Editors-in-Chief. The publication of individual uninvited original research articles can be sent to our sister journal Catalysis Letters. This journal aims for rapid publication of high-impact original research articles in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis.