Synthesis and reactivity of dinuclear CpRu tert-butylamido and cyclometallated Bis(trimethylsilyl)amido complexes

Synthesis and reactivity of dinuclear CpRu tert-butylamido and cyclometallated Bis(trimethylsilyl)amido complexes

Treatment of [Cp*Ru(μ3-Cl)]4 with 4 equiv of LiNHtBu in THF produces the dimeric tert-butylamido complex [Cp*Ru(μ-NHtBu)]2 (1b) in 85% yield. Complex 1b reacts with Ph2SCH2 and CNtBu to give the imido methylene complex (Cp*Ru)2(μ-NtBu)(μ-CH2) (2b) and the bis(amido) bis(isocyanide) complex [Cp*Ru(CN...

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Bibliographic Details
Published in:Journal of organometallic chemistry Vol. 797; pp. 60 - 66
Main Authors: Takemoto, Shin, Oshimo, Masaki, Matsuzaka, Hiroyuki
Format: Journal Article
Language:English
Published: Elsevier B.V 15-11-2015
Subjects:
Amido complex
Cyclometallation
Imido complex
Ruthenium
Silylamido ligand
Ruthenium
Silylamido ligand
Cyclometallation
Amido complex
Imido complex
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Summary:Treatment of [Cp*Ru(μ3-Cl)]4 with 4 equiv of LiNHtBu in THF produces the dimeric tert-butylamido complex [Cp*Ru(μ-NHtBu)]2 (1b) in 85% yield. Complex 1b reacts with Ph2SCH2 and CNtBu to give the imido methylene complex (Cp*Ru)2(μ-NtBu)(μ-CH2) (2b) and the bis(amido) bis(isocyanide) complex [Cp*Ru(CNtBu)(μ-NHtBu)]2 (3b), respectively. The reaction of [Cp*Ru(μ3-Cl)]4 with 4 equiv of NaN(SiMe3)2 proceeds via double C–H activation of a SiMe group to give the cyclometallated silylamido complex (Cp*Ru)2(μ-H)(μ-HCSiMe2NSiMe3) (4) in 91% yield. Single-crystal X-ray analysis and low-temperature 1H and 13C NMR spectroscopy for 4 reveal the amido-carbene formulation of the cyclometallated ligand. Variable-temperature NMR analysis for 4 reveals a rapid exchange of the hydride and carbene protons and indicates a reversible C–H reductive coupling between the silylcarbene and the hydride moieties, which has been reasonably modeled by DFT calculations. [Display omitted] •Reactions of [Cp*Ru(μ3-Cl)]4 with LiNHtBu and NaN(SiMe3)2.•Synthesis of dinuclear amido, imido, and cyclometallated silyamido complexes.•Reversible C–H reductive coupling in the cyclometallated complex.
ISSN:0022-328X
1872-8561
DOI:10.1016/j.jorganchem.2015.07.042