Preferential Photoreaction in a Porous Crystal, Metal-Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition.
Preferential Photoreaction in a Porous Crystal, Metal-Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition.
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DOI：
10.1021/jacs.8b08534
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发表时间：
2018-11
影响因子：
15
通讯作者：
Hirotaka Yonezawa;S. Tashiro;Takafumi Shiraogawa;M. Ehara;Rintaro Shimada;T. Ozawa;M. Shionoya
中科院分区：
文献类型：
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作者：
Hirotaka Yonezawa;S. Tashiro;Takafumi Shiraogawa;M. Ehara;Rintaro Shimada;T. Ozawa;M. Shionoya
具有明确功能表面的纳米级密闭空间在控制催化反应的效率和选择性方面具有很大的潜力。本文报道了1,6-二烯在光照射下通常形成分子内[2+2]环加合物，在多孔晶体金属-大环框架（MMF）中优先发生光诱导烯烃迁移，并且在密闭空间中完全抑制[2+2]环加成。基于uv -可见漫反射光谱、单晶XRD和MS-CASPT2计算，提出了光诱导Pd-Cl键离解引发烯烃迁移的合理反应机理。用取代烯基苯衍生物考察了光致烯烃在MMF中迁移的底物范围。
A nanosized confined space with well-defined functional surfaces has great potential to control the efficiency and selectivity of catalytic reactions. Herein we report that a 1,6-diene, which normally forms an intramolecular [2+2] cycloadduct under photoirradiation, preferentially undergoes a photoinduced olefin migration in a porous crystal, metal-macrocycle framework (MMF), and alternatively [2+2] cycloaddition is completely inhibited in the confined space. A plausible reaction mechanism for olefin migration triggered by the photoinduced dissociation of the Pd-Cl bond is suggested based on UV-vis diffuse reflectance spectroscopy, single-crystal XRD, and MS-CASPT2 calculation. The substrate scope of the photoinduced olefin migration in MMF was also examined using substituted allylbenzene derivatives.