Abstract

In contrast to heterogeneous network frameworks (e.g., covalent organic frameworks and metal-organic frameworks) and porous organic polymers, porous organic cages (POCs) are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis. Herein, we report a triphenylphosphine-derived quasi-porous organic cage (denoted as POC-DICP) as an efficient organic molecular cage ligand for Rh/PPh₃ system-catalyzed homogeneous hydroformylation reactions. POC-DICP not only displays enhanced hydroformylation selectivity (aldehyde selectivity as high as 97% and a linear-to-branch ratio as high as 1.89) but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems. We speculate that the reason for the high activity and good selectivity is the favorable geometry (cone angle = 123.88°) and electronic effect (P site is relatively electron-deficient) of POC-DICP, which were also demonstrated by density functional theory calculations and X-ray absorption fine-structure characterization.

中文翻译：

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通过开发PPh ₃衍生的准多孔有机笼作为配体，增强Rh / PPh ₃系统催化的加氢甲酰化反应的活性，选择性和可回收性

摘要

与异质网络框架（例如，共价有机框架和金属有机框架）和多孔有机聚合物相反，多孔有机笼（POC）是常见有机溶剂中的可溶性分子，为均相催化提供了巨大潜力。在此，我们报道了三苯基膦衍生的准多孔有机笼（表示为POC-DICP）作为Rh / PPh ₃的有效有机分子笼配体系统催化的均相加氢甲酰化反应。POC-DICP不仅显示出更高的加氢甲酰化选择性（醛选择性高达97％，线性支化比高达1.89），而且可以通过简单的沉淀方法在均相反应系统中进行回收和再利用。我们推测POC-DICP的良好几何形状（锥角= 123.88°）和电子效应（P位相对电子不足）是高活性和高选择性的原因，这也由密度泛函理论计算和X射线吸收精细结构表征。