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Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metal–organic framework
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-06-01 , DOI: 10.1039/d3dt01403g Hongrui Tian 1 , Runhan Li 2 , Jun Miao 1 , Shuxia Liu 3 , Fengfeng Wang 4 , Zhiping Zheng 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2023-06-01 , DOI: 10.1039/d3dt01403g Hongrui Tian 1 , Runhan Li 2 , Jun Miao 1 , Shuxia Liu 3 , Fengfeng Wang 4 , Zhiping Zheng 1
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Selective oxidation of alcohols to aldehydes is an industrially significant chemical transformation. Herein, we report a mixed-valence polyoxovanadate-based metal–organic framework (MOF), (H2bix)5{[Cd(bix)2][VIV8VV7O36Cl]2}·3H2O (V-Cd-MOF), for catalyzing the additive-free oxidation of a series of aromatic alcohols with high selectivity and in nearly quantitative yield to the corresponding aldehydes with O2 as the oxidant. Experimental results, corroborated with density functional theory calculations, indicate that it is the synergistic operation of the dual active sites of the VIV–O–VV building units in the polyoxovanadate cluster that is responsible for the excellent catalytic performance observed: on the one hand, the exposed and readily accessible reduced VIV site is believed to activate O2, resulting in a reactive oxygen species for the subsequent activation and breaking of the substrate's Cα–H bond. On the other hand, the VV site coordinates with the alcoholic O atom to facilitate the cleavage of the O–H bond. The catalyst can be recycled by centrifugation and re-used at least five times with uncompromised performance. To our knowledge, V-Cd-MOF represents the first example of a polyoxometalate-based MOF catalyst for additive-free selective oxidation of alcohol to aldehyde with O2 as an oxidant.
中文翻译：
混合价多钒酸盐金属有机骨架催化芳香醇与分子氧的无添加剂选择性氧化
醇选择性氧化为醛是工业上重要的化学转化。在此，我们报道了一种混合价多钒酸盐基金属有机骨架材料（MOF），(H 2 bix) 5 {[Cd(bix) 2 ][V IV 8 V V 7 O 36 Cl ] 2 }·3H 2 O ( V-Cd-MOF )，用于催化一系列芳香醇与 O 2进行无添加剂氧化，高选择性且几乎定量收率生成相应的醛作为氧化剂。密度泛函理论计算证实的实验结果表明，多氧钒酸盐团簇中 V IV –O–V V结构单元的双活性位点的协同作用导致了所观察到的优异催化性能：一方面另一方面，暴露且易于接近的还原V IV位点被认为会激活O 2，从而产生活性氧物质，用于随后激活和破坏底物的C α -H 键。另一方面，VV位点与醇O原子配位以促进O-H键的断裂。该催化剂可通过离心回收并重复使用至少五次，且性能不受影响。据我们所知，V-Cd-MOF代表了基于多金属氧酸盐的MOF催化剂的第一个例子，用于以O 2作为氧化剂将醇无添加剂选择性氧化为醛。
更新日期：2023-06-01
中文翻译：
混合价多钒酸盐金属有机骨架催化芳香醇与分子氧的无添加剂选择性氧化
醇选择性氧化为醛是工业上重要的化学转化。在此，我们报道了一种混合价多钒酸盐基金属有机骨架材料（MOF），(H 2 bix) 5 {[Cd(bix) 2 ][V IV 8 V V 7 O 36 Cl ] 2 }·3H 2 O ( V-Cd-MOF )，用于催化一系列芳香醇与 O 2进行无添加剂氧化，高选择性且几乎定量收率生成相应的醛作为氧化剂。密度泛函理论计算证实的实验结果表明，多氧钒酸盐团簇中 V IV –O–V V结构单元的双活性位点的协同作用导致了所观察到的优异催化性能：一方面另一方面，暴露且易于接近的还原V IV位点被认为会激活O 2，从而产生活性氧物质，用于随后激活和破坏底物的C α -H 键。另一方面，VV位点与醇O原子配位以促进O-H键的断裂。该催化剂可通过离心回收并重复使用至少五次，且性能不受影响。据我们所知，V-Cd-MOF代表了基于多金属氧酸盐的MOF催化剂的第一个例子，用于以O 2作为氧化剂将醇无添加剂选择性氧化为醛。
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