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钌/镓配合物上的碳-氢键和硅-氢键活化反应：关于钌-镓键的实验与理论相结合的案例研究

C-H and Si-H Activation Reactions at Ru/Ga Complexes: A Combined Experimental and Theoretical Case Study on the Ru-Ga Bond.

作者信息

Muhr Maximilian, Bühler Raphael, Liang Hao, Gilch Jonas, Jandl Christian, Kahlal Samia, Saillard Jean-Yves, Gemel Christian, Fischer Roland A

机构信息

Chair of Inorganic and Metalorganic Chemistry, Department of Chemistry, Catalysis Research Center (CRC), Technical University Munich (TUM), Lichtenbergstraße 4, 85748, Garching, Germany.

UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Univ Rennes, CNRS, ISCR-UMR 6226, 35000, Rennes, France.

出版信息

Chemistry. 2022 Sep 27;28(54):e202200887. doi: 10.1002/chem.202200887. Epub 2022 Aug 3.

DOI:10.1002/chem.202200887
PMID:35748293
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9804459/
Abstract

Treatment of [Ru(COD)(MeAllyl) ] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to reactive intermediates which activate Si-H or C-H bonds, respectively. The product complexes [Ru(GaCp*) (SiEt )H ] (1) and [Ru(GaCp*) (C H )H ] (2) are formed with HSiEt or with toluene as the solvent, respectively. While 1 was isolated and fully characterized by NMR, MS, IR and SC-XRD, 2 was too labile to be isolated and was observed and characterized in situ by using mass spectrometry, including labelling experiments for the unambiguous assignment of the elemental composition. The structural assignment was confirmed by DFT calculations. The relative energies of the four isomers possible upon toluene activation at the ortho-, meta-, para- and CH -positions have been determined and point to aromatic C-H activation. The Ru-Ga bond was analyzed by EDA and QTAIM and compared to the Ru-P bond in the analogue phosphine compound. Bonding analyses indicate that the Ru-GaCp* bond is weaker than the Ru-PR bond.

摘要

在氢解条件下，用茂镓（GaCp*）处理[Ru(COD)(MeAllyl)]和[Ru(COD)(COT)]会分别生成能活化硅氢键或碳氢键的活性中间体。产物配合物[Ru(GaCp*)(SiEt₃)H]（1）和[Ru(GaCp*)(C₆H₅)H]（2）分别以三乙基硅烷（HSiEt₃）或甲苯为溶剂生成。虽然配合物1已通过核磁共振（NMR）、质谱（MS）、红外光谱（IR）和单晶X射线衍射（SC-XRD）进行了分离和全面表征，但配合物2太不稳定，无法分离，通过质谱原位观察和表征，包括用于明确元素组成归属的标记实验。结构归属通过密度泛函理论（DFT）计算得到证实。已确定了甲苯在邻位、间位、对位和甲基位置活化时可能产生的四种异构体的相对能量，表明发生了芳环碳氢键活化。通过能量分解分析（EDA）和量子拓扑原子分子理论（QTAIM）对钌-镓键进行了分析，并与类似膦化合物中的钌-磷键进行了比较。键合分析表明，钌-茂镓键（Ru-GaCp*）比钌-膦键（Ru-PR）弱。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/067f8f896186/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/bd4e172ae05f/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/1507d38f8970/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/93e9165a072c/CHEM-28-0-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/067f8f896186/CHEM-28-0-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/bd4e172ae05f/CHEM-28-0-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/1507d38f8970/CHEM-28-0-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/93e9165a072c/CHEM-28-0-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6370/9804459/067f8f896186/CHEM-28-0-g005.jpg

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