Guoqing Wang, Miao Jiang, Benhan Fan, Zhao Sun, Leilei Qian, Guangjun Ji, Lei Ma, Cunyao Li, Zhaozhan Wang, Guifa Long*, Yong Yang*, Li Yan* and Yunjie Ding*,
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引用次数: 0
摘要
通过加氢甲酰化/加氢反应从醋酸乙烯中提取 1,3-丙二醇一直被认为是替代现有技术的最有前途的策略。迄今为止,乙酸乙烯酯加氢甲酰化的线性醛的区域选择性还远远不能令人满意。在此,我们制备了一系列具有约束效应的单位催化剂,其中不同的第二壳原子(C、O 和 N)与 P 原子键合。Rh-P-N-POPs 催化剂(其中两个 N 原子和一个 O 原子与一个 P 原子键合)不仅具有良好的醛产率,而且具有诱人的区域选择性(l/b = 1.5),优于 Rh-P-C-POPs(l/b = 0.007)、Rh-P-O-POPs(l/b = 0.01)以及之前报道的所有优化 Rh 催化剂(l/b = 0.8)。表征和 DFT 计算表明,性能的提高主要归因于禁锢效应和缺电子特性所产生的选择性结合。配体产生的约束效应阻碍了醋酸盐的螯合作用,促进了 Rh 与烯烃末端碳的选择性结合。同时,Rh-P-N-POPs 催化剂中作为第二壳原子的 N 赋予 Rh 活性位点缺电子配位环境,加快了线性醛的形成速率。这项工作提供了一种利用第二壳原子的约束效应调节加氢甲酰化性能的有效策略,为设计具有高区域选择性的异质催化剂用于功能烯烃的加氢甲酰化提供了启示。
Selective Association Enforced by the Confinement Effect To Boost the Regioselectivity of Vinyl Acetate Hydroformylation
1,3-Propanediol derived from vinyl acetate through hydroformylation/hydrogenation has always been considered the most promising strategy to substitute the current technology. So far, the linear aldehyde regioselectivity of vinyl acetate hydroformylation is still far from satisfactory. Herein, we prepare a series of single-site catalysts with a confinement effect, in which different second-shell atoms (C, O, and N) are bonded with the P atom. The Rh–P–N-POPs catalyst, in which two N and one O atoms are bonded with a P atom, delivers not only a good aldehyde yield but also attractive regioselectivity (l/b = 1.5), outperforming Rh–P–C-POPs (l/b = 0.007), Rh–P–O-POPs (l/b = 0.01), and all previously reported optimizing Rh catalysts (l/b = 0.8). Characterizations and DFT calculations suggest that the enhanced performance is mainly ascribed to selective association enforced by the confinement effect and electron-deficient properties. The confinement effect, which is imposed by the ligand, hinders the chelating effect of acetate and facilitates the selective association of Rh with the terminal carbon of olefins. Meanwhile, N as second-shell atoms in the Rh–P–N-POPs catalyst endows Rh active sites with an electron-deficient coordination environment and accelerates the linear aldehyde forming rate. This work offers an effective strategy to regulate the hydroformylation performance by the confinement effect for the modulation of a second-shell atom, which sheds light on designing heterogeneous catalysts with high regioselectivity for the hydroformylation of functional olefins.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.