Zhang Zhong, Ma Xujiao, Li Yameng, Ma Nana, Wang Ming, Liu Wei, Peng Jiahui, Liu Yiwei, Li Yadong
School of Chemistry, Dalian University of Technology Dalian 116024, China.
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
J Am Chem Soc. 2024 Mar 27;146(12):8425-8434. doi: 10.1021/jacs.3c14296. Epub 2024 Mar 15.
The precise design of catalytic metal centers with multiple chemical states to facilitate sophisticated reactions involving multimolecular activation is highly desirable but challenging. Herein, we report an ordered macroporous catalyst with heterovalent metal pair (HMP) sites comprising Cu-Cu on the basis of a microporous metal-organic framework (MOF) system. This macroporous HMP catalyst with proximity heterovalent dual copper sites, whose distance is controlled to ∼2.6 Å, on macropore surface exhibits a co-activation behavior of ethanol at Cu and alkyne at Cu, and avoids microporous restriction, thereby promoting additive-free alkyne hydroboration reaction. The desired yield enhances dramatically compared with the pristine MOF and ordered macroporous MOF both with solely isovalent Cu-Cu sites. Density functional theory calculations reveal that the Cu-HMP sites can stabilize the Bpin-Cu-Cu-alkyne intermediate and facilitate C-B bond formation, resulting in a smooth alkyne hydroboration process. This work provides new perspectives to design multimolecular activation catalysts for sophisticated matter transformations.
精确设计具有多种化学状态的催化金属中心以促进涉及多分子活化的复杂反应是非常理想的，但具有挑战性。在此，我们基于微孔金属有机框架（MOF）体系报道了一种具有包含Cu-Cu的异价金属对（HMP）位点的有序大孔催化剂。这种在大孔表面具有距离控制在约2.6 Å的邻近异价双铜位点的大孔HMP催化剂表现出乙醇在Cu位点和炔烃在Cu位点的共活化行为，并避免了微孔限制，从而促进了无添加剂的炔烃硼氢化反应。与仅具有同价Cu-Cu位点的原始MOF和有序大孔MOF相比，所需产率显著提高。密度泛函理论计算表明，Cu-HMP位点可以稳定Bpin-Cu-Cu-炔烃中间体并促进C-B键的形成，从而实现炔烃硼氢化过程的顺利进行。这项工作为设计用于复杂物质转化的多分子活化催化剂提供了新的视角。
