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Updated: Jan 17, 2026

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
Published on: August 23, 2018
Ruthenium-Promoted Acceptor-less Dehydrogenation of a Germane
Aidan F Carr-Davis1, Aswin Chandran1,2, Theo F N Tanner1
1Department of Chemistry, University of York, Heslington, York, North Yorkshire, YO10 5DD, UK.
Abstract:
The transition metal-mediated activation of element-hydrogen bonds is an important goal for the preparation of commodity chemical compounds and novel materials. Here a facile route to the activation of germanium-hydrogen bonds, based on the spontaneous elimination of dihydrogen, is reported. This represents a mechanistic divergence from the established methods for Ge─H bond cleavage. The novel complexes [Ru(η5-C5H5)(OTf)(PPh3)2] and [{Ru(η5-C5H5)(dppe)}2(μ-N2)]OTf2 are central to the success of this route. These crystalline species may be prepared in high yield and are highly effective sources of the 16-electron [Ru(η5-C5H5)(P)2]+ fragment. Both complexes react with GeH2Ph2 to eliminate H2 and afford [Ru(η5-C5H5)(GePh2OTf)(P)2] [(P)2 = 2 PPh3, dppe], which is best described as a triflate-stabilized metallogermylenium complex. Different species are observed on initial treatment of [Ru(η5-C5H5)(OTf)(PPh3)2] or [{Ru(η5-C5H5)(dppe)}2(μ-N2)]OTf2 with GeH2Ph2. In the dppe case, a σ-germane complex is identified, which is proposed to undergo spontaneous elimination of H2: a key step in the double Ge─H bond activation, promoted by the sterically demanding half-sandwich ruthenium complexes. This represents a distinct pathway for Ge─H bond activation when compared to the established routes, such as deprotonation by a basic hydrocarbyl ligand or oxidative addition, leading the way to new pathways to functionalize organogermanium compounds.
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