A stable and structurally well-defined titanium alkoxide catalyst supported on a metal–organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OⁱPr)₂) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OⁱPr)₂ is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. In addition, ANL1-Ti(OⁱPr)₂ catalyst exhibits remarkable hydroboration selectivity toward aldehydes vs ketone in competitive study. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate-determining step) and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the borate ester product.

中文翻译：

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金属-有机骨架上支持羰基化合物硼氢化的单点Ti（IV）

合成了稳定且结构明确的烷氧基钛醇盐催化剂，该催化剂负载在UiO-67拓扑结构的金属有机框架（MOF）（ANL1-Ti（O ⁱ Pr）₂）上，并通过多种分析和光谱技术进行了全面表征，包括BET，TGA，PXRD，XAS，DRIFT，SEM和DFT计算。钛功能化的MOF被证明对使用HBpin作为硼源的各种醛和酮的催化加氢硼化具有活性。与传统的均相和负载型硼氢化催化剂相比，ANL1-Ti（O ⁱ Pr）₂可以完全回收利用和再利用，使其成为绿色和可持续化学合成的有希望的硼氢化催化剂替代品。此外，在竞争研究中，ANL1-Ti（O ⁱ Pr）₂催化剂对醛类和酮类具有显着的硼氢化选择性。DFT计算表明，催化氢硼化反应是通过（1）活性Ti-氢化物与羰基部分之间的氢化物转移（速率确定步骤）和（2）醇盐转移（分子内σ键复分解）生成硼酸酯而进行的。产品。