Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal-Macrocycle Framework
Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal-Macrocycle Framework
复制标题
多孔晶体金属大环骨架 Pd(II) 中心光致催化烯烃迁移反应的机理研究
DOI：
10.1002/asia.202001306
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
M. Shionoya
中科院分区：
文献类型：
--
作者：
H. Yonezawa;T. Shiraogawa;M. Han;S. Tashiro;M. Ehara;M. Shionoya
孔表面具有明确的活性金属中心的多孔晶体具有作为非均相金属催化剂的巨大潜力。我们最近证明，多孔分子晶体金属大环骨架（MMF）通过暴露在晶体通道表面上的 PdIICl2 部分的光活化来催化烯烃迁移反应。在此，我们报告了 MMF PdII 活性中心光诱导烯烃迁移反应的机理研究。包括氘扰乱研究在内的多项实验表明，在光照射过程中，通道表面上原位生成的 Pd−H 物质通过烷基机制催化烯烃迁移。该机制得到了 DFT 和 ONIOM 计算的进一步支持。
Porous crystals with well‐defined active metal centers on the pore surface have high potential as heterogeneous metal catalysts. We have recently demonstrated that a porous molecular crystal, metal‐macrocycle framework (MMF), catalyzes olefin migration reactions by photoactivation of its PdIICl2moieties exposed on the crystalline channel surface. Herein we report a mechanistic study of the photoinduced olefin migration reactions at the PdIIactive centers of MMF. Several experiments, including a deuterium scrambling study, revealed that olefin migration is catalyzedviaan alkyl mechanism byinsitugenerated Pd−H species on the channel surface during photoirradiation. This proposed mechanism was further supported by DFT and ONIOM calculations.