Step-by-Step Introduction of Silazane Moieties at Ruthenium: Different Extents of Ru鈥揌鈥揝i Bond Activation

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• 作者：Katharine A. Smart ; Mary Grellier ; Laure Vendier ; Sax A. Mason ; Silvia C. Capelli ; Alberto Albinati ; Sylviane Sabo-Etienne
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：March 4, 2013
• 年：2013
• 卷：52
• 期：5
• 页码：2654-2661
• 全文大小：364K
• 年卷期：v.52,no.5(March 4, 2013)
• ISSN：1520-510X

文摘

The coordination of pyridine-2-amino(methyl)dimethylsilane ligands to ruthenium has afforded access to a family of novel complexes that display multicenter Ru鈥揌鈥揝i interactions according to the number of incorporated ligands. The new complexes Ru[魏-Si,N-(SiMe₂)N(Me)(C₅H₄N)](畏⁴-C₈H₁₂)(畏³-C₈H₁₁) (1), Ru₂(渭-H)₂(H)₂[魏-Si,N-(SiMe₂)N(Me)(C₅H₄N)]₄ (2), and Ru(H)[魏-Si,N-(SiMe₂)N(Me)(C₅H₄N)]₃ (3) were isolated and fully characterized. The complexes exhibit different degrees of Si鈥揌 activation: complete Si鈥揌 cleavage, secondary interactions between the atoms (SISHA), and 畏²-Si鈥揌 coordination. Reversible protonation of 3 leading to the cationic complex [RuH{(畏²-H-SiMe₂)N(Me)魏-N-(C₅H₄N)}{魏-Si,N-(SiMe₂)N(Me)(C₅H₄N)}₂]⁺[BAr^F₄]^{鈭?/sup> (5) was also demonstrated. The coordination modes in these systems were carefully studied with a combination of X-ray and neutron diffraction analysis, DFT geometry optimization, and multinuclear NMR spectroscopy.}