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Highly Stable Polyoxovanadate-Based Zn–MOF with Dual Active Sites as a Solvent-free Catalyst for C–C Bond Formation
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2021-03-17 , DOI: 10.1021/acssuschemeng.1c00389 Hongrui Tian 1 , Shumei Liu 1 , Zhong Zhang 1 , Tianyi Dang 1 , Ying Lu 1 , Shuxia Liu 1
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2021-03-17 , DOI: 10.1021/acssuschemeng.1c00389 Hongrui Tian 1 , Shumei Liu 1 , Zhong Zhang 1 , Tianyi Dang 1 , Ying Lu 1 , Shuxia Liu 1
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A polyoxovanadate-based zinc–organic framework, [Zn(bix)]{V2O6}(V-Zn-MOF, bix = 1,4-bis(imidazole-1-ylmethyl)benzene), was successfully synthesized under hydrothermal conditions. Single-crystal X-ray analysis reveals that the V-Zn-MOF contains {V2O6}n2n– polyanion chains and [Zn(bix)]2+ cation frameworks with open zinc metal sites, which endows V-Zn-MOF-rich Lewis base and acid sites. Considering that Lewis acid and base can usually be utilized as active centers for catalytic reactions, we explore the catalytic activity of the V-Zn-MOF for Knoevenagel condensation and cyanosilylation of aromatic aldehydes. The experimental results indicate that the V-Zn-MOF can efficiently and selectively catalyze both reactions of the Knoevenagel condensation and cyanosilylation of aromatic aldehydes under solvent-free conditions, which is attributed to the two-site synergetic effect: (1) the open zinc site as a Lewis acid catalyst can electrophilically activate the carbonyl group of aldehydes; (2) the {V2O6}n2n– polyanion as a Lewis base catalyst can activate methylene or cyanating reagents through the nucleophilic reaction. In addition, the connection mode of {V2O5}–O–Zn closes the molecular size distance between the two activated substrates, thereby improving efficiency of the catalytic reaction. More importantly, the V-Zn-MOF exhibits excellent sustainability, no obvious decrease in the catalytic activity is observed in both catalytic reactions after 10 cycles. These results manifest that the V-Zn-MOF has great potential for practical application in C–C bond formation.
中文翻译：
具有双活性位的高度稳定的基于聚氧钒酸盐的Zn-MOF，作为无溶剂的CC键形成催化剂
在水热条件下成功合成了基于聚氧钒酸盐的锌-有机骨架[Zn（bix）] {V 2 O 6 }（V-Zn-MOF，bix = 1,4-双（咪唑-1-基甲基）苯）。条件。X射线单晶分析表明，V-Zn-MOF含有{V 2 O 6 } n 2 n –聚阴离子链和[Zn（bix）] 2+具有开放锌金属位点的阳离子骨架，赋予了富含V-Zn-MOF的Lewis碱和酸性位点。考虑到路易斯酸和碱通常可以用作催化反应的活性中心，我们探讨了V-Zn-MOF对Knoevenagel缩合和芳族醛的氰基硅烷化的催化活性。实验结果表明，在无溶剂条件下，V-Zn-MOF能够高效，选择性地催化芳族醛的Knoevenagel缩合反应和氰基硅烷化反应，这归因于两点协同作用：（1）开口锌路易斯酸催化剂的位点可以亲电活化醛的羰基; （2）{V 2 O 6 } n 2 n –作为路易斯碱催化剂的聚阴离子可以通过亲核反应活化亚甲基或氰化试剂。此外，{V 2 O 5 } –O–Zn的连接模式缩短了两个活化底物之间的分子大小距离，从而提高了催化反应的效率。更重要的是，V-Zn-MOF显示出优异的可持续性，在10个循环后的两个催化反应中均未观察到催化活性的明显降低。这些结果表明，V-Zn-MOF在C–C键形成中具有实际应用的巨大潜力。
更新日期：2021-03-29
中文翻译：
具有双活性位的高度稳定的基于聚氧钒酸盐的Zn-MOF，作为无溶剂的CC键形成催化剂
在水热条件下成功合成了基于聚氧钒酸盐的锌-有机骨架[Zn（bix）] {V 2 O 6 }（V-Zn-MOF，bix = 1,4-双（咪唑-1-基甲基）苯）。条件。X射线单晶分析表明，V-Zn-MOF含有{V 2 O 6 } n 2 n –聚阴离子链和[Zn（bix）] 2+具有开放锌金属位点的阳离子骨架，赋予了富含V-Zn-MOF的Lewis碱和酸性位点。考虑到路易斯酸和碱通常可以用作催化反应的活性中心，我们探讨了V-Zn-MOF对Knoevenagel缩合和芳族醛的氰基硅烷化的催化活性。实验结果表明，在无溶剂条件下，V-Zn-MOF能够高效，选择性地催化芳族醛的Knoevenagel缩合反应和氰基硅烷化反应，这归因于两点协同作用：（1）开口锌路易斯酸催化剂的位点可以亲电活化醛的羰基; （2）{V 2 O 6 } n 2 n –作为路易斯碱催化剂的聚阴离子可以通过亲核反应活化亚甲基或氰化试剂。此外，{V 2 O 5 } –O–Zn的连接模式缩短了两个活化底物之间的分子大小距离，从而提高了催化反应的效率。更重要的是，V-Zn-MOF显示出优异的可持续性，在10个循环后的两个催化反应中均未观察到催化活性的明显降低。这些结果表明，V-Zn-MOF在C–C键形成中具有实际应用的巨大潜力。
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