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Inorg Chem. 2013 Mar 4;52(5):2654-61. doi: 10.1021/ic302682f. Epub 2013 Feb 19.

Step-by-step introduction of silazane moieties at ruthenium: different extents of Ru-H-Si bond activation.

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1
LCC (Laboratoire de Chimie de Coordination), CNRS, 205 Route de Narbonne, F-31077 Toulouse, France.

Abstract

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)](η(4)-C8H12)(η(3)-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 η(2)-Si-H coordination. Reversible protonation of 3 leading to the cationic complex [RuH{(η(2)-H-SiMe2)N(Me)κ-N-(C5H4N)}{κ-Si,N-(SiMe2)N(Me)(C5H4N)}2](+)[BAr(F)4](-) (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.

PMID:
23421738
DOI:
10.1021/ic302682f
[Indexed for MEDLINE]
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