Step-by-Step Introduction of Silazane Moieties at Ruthenium: Different Extents of Ru–H–Si Bond Activation

Katharine Smart (1, 2) , Mary Grellier (1, 2) , Laure Vendier (1, 2) , Sax Mason (3) , Silvia Capelli (3) , Alberto Albinati (4) , Sylviane Sabo-Etienne (1, 2)

1 LCC - Laboratoire de chimie de coordination
2 UT3 - Université Toulouse III - Paul Sabatier
3 ILL - Institut Laue-Langevin
4 Dipartimento di Chimica

The coordination of pyridine-2-amino(methyl)dimethylsilane ligands to ruthenium has afforded access to a family of novel complexes that display multicenter Ru–H–Si interactions according to the number of incorporated ligands. The new complexes Ru[κ-Si,N-(SiMe2)N(Me)(C5H4N)](η4-C8H12)(η3-C8H11) (1), Ru2(μ-H)2(H)2[κ-Si,N-(SiMe2)N(Me)(C5H4N)]4 (2), and Ru(H)[κ-Si,N-(SiMe2)N(Me)(C5H4N)]3 (3) were isolated and fully characterized. The complexes exhibit different degrees of Si–H activation: complete Si–H cleavage, secondary interactions between the atoms (SISHA), and η2-Si–H coordination. Reversible protonation of 3 leading to the cationic complex [RuH{(η2-H-SiMe2)N(Me)κ-N-(C5H4N)}{κ-Si,N-(SiMe2)N(Me)(C5H4N)}2]+[BArF4]− (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.

Domaines: Chimie de coordination

Katharine Smart, Mary Grellier, Laure Vendier, Sax Mason, Silvia Capelli, et al.. Step-by-Step Introduction of Silazane Moieties at Ruthenium: Different Extents of Ru–H–Si Bond Activation. Inorganic Chemistry, 2013, 52 (5), pp.2654-2661. ⟨10.1021/ic302682f⟩. ⟨hal-02908574⟩