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Extension of the Surface Organometallic Chemistry to Metal-Organic Framework: development of well-defined single site [(≡Zr-O-)W(=O)(CH2tBu)3] olefin metathesis catalyst.
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-09-09 , DOI: 10.1021/jacs.0c06925
Zeynabou Thiam 1, 2, 3 , Edy Abou-Hamad 4 , Busra Dereli 3 , Lingmei Liu 1 , Abdul-Hamid Emwas 4 , Rafia Ahmad 3 , Hao Jiang 1, 2 , Abdulrahman Adamu Isah 5 , Papa Birame Ndiaye 6 , Mostafa Taoufik 5 , Yu Han 1 , Luigi Cavallo 3 , Jean-Marie Basset 3 , Mohamed Eddaoudi 1, 2
Affiliation  

We report here the first step by step anchoring of a W(≡CtBu)(CH2tBu)3 complex on a highly crystalline and mesoporous MOF, namely Zr-NU-1000, using Surface organometallic Chemistry (SOMC) concept and methodology. SOMC allowed us to selectively graft the complex on the Zr6 clusters and characterize the obtained single site material by using state of the art experimental methods including extensive solid-state NMR techniques and HAADF-STEM imaging. Further FT-IR spectroscopy revealed the presence of a W=O moiety arising from the in situ reaction of the W≡CtBu functionality with the coordinated water coming from the 8-connected hexanuclear Zr6 clusters. All the steps leading to the final grafted molecular complex have been identified by DFT. The obtained material was tested for gas phase and liquid phase olefin metathesis and exhibited higher catalytic activity than the corresponding catalysts synthesized by different grafting methods. This contribution establishes the importance of applying SOMC to MOF chemistry to get well defined single site catalyst on MOF inorganic secondary building units, in particular the in situ synthesis of W=O alkyl complexes from their W carbyne analogues.

中文翻译:

将表面有机金属化学扩展到金属-有机框架:开发明确定义的单中心 [(≡Zr-O-)W(=O)(CH2tBu)3] 烯烃复分解催化剂。

我们在此报告了使用表面有机金属化学 (SOMC) 概念和方法将 W(≡CtBu)(CH2tBu)3 复合物固定在高度结晶和介孔 MOF,即 Zr-NU-1000 上的第一步。SOMC 允许我们在 Zr6 簇上选择性地接枝复合物,并通过使用最先进的实验方法(包括广泛的固态 NMR 技术和 HAADF-STEM 成像)表征获得的单点材料。进一步的 FT-IR 光谱揭示了 W=O 部分的存在,这是由 W≡CtBu 官能团与来自 8 个连接的六核 Zr6 簇的配位水的原位反应产生的。通向最终接枝分子复合物的所有步骤都已通过 DFT 确定。所得材料经气相和液相烯烃复分解测试,表现出比通过不同接枝方法合成的相应催化剂更高的催化活性。这一贡献确立了将 SOMC 应用于 MOF 化学以在 MOF 无机二级构建单元上获得明确定义的单中心催化剂的重要性,特别是从它们的 W 碳炔类似物原位合成 W=O 烷基配合物。
更新日期:2020-09-09
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