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

被引：11

作者：

Muhr, Maximilian ^{[1
]}

Buhler, Raphael ^{[1
]}

Liang, Hao ^{[2
]}

Gilch, Jonas ^{[1
]}

Jandl, Christian ^{[1
]}

Kahlal, Samia ^{[2
]}

Saillard, Jean-Yves ^{[2
]}

Gemel, Christian ^{[1
]}

Fischer, Roland A. ^{[1
]}

机构：

[1] Tech Univ Munich TUM, Catalysis Res Ctr CRC Tech, Dept Chem, Chair Inorgan & Metalorgan Chem, Lichtenbergstr 4, D-85748 Garching, Germany

[2] Univ Rennes, UMR CNRS, 6226 Inst Sci Chim Rennes, CNRS,ISCR UMR 6226, F-35000 Rennes, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2022年 / 28卷 / 54期

关键词：

bond activation; cluster intermediates; density functional calculations; intermetallic compounds; mass spectrometry; TRANSITION-METAL-COMPLEXES; RUTHENIUM COMPLEXES; CO2; HYDROGENATION; ENERGY; EXCHANGE; LIGANDS; GALLIUM; HYDROSILYLATION; APPROXIMATION; DERIVATIVES;

D O I：

10.1002/chem.202200887

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of [Ru(COD)(MeAllyl)(2)] 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*)(3)(SiEt3)H-3] (1) and [Ru(GaCp*)(3)(C7H7)H-3] (2) are formed with HSiEt3 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 CH3-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-PR3 bond.

引用

页数：6

共 66 条

[11] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].