Synthesis of a heterometallic spiked tetrahedral cluster of ruthenium and nickel containing multiple hydrido ligands and its degradation to a tetrahedral NiRu3 cluster

Publication date: Available online 28 December 2018Source: Journal of Organometallic ChemistryAuthor(s): Takuya Kosukegawa, Toshiro TakaoAbstractA bimetallic spiked tetrahedral cluster of Ni and Ru, {Cp*Ru(H)(μ-H)3}-{Ni(Cp*Ru)3(μ3-H)3(μ-H)3} (2) (Cp* = η5-C5Me5), was synthesized by reaction of Cp*Ru(μ-H)4RuCp* (1) with Ni(cod)2 under an atmosphere of H2. Cluster 2 comprises monomeric (Cp*RuH) and tetrahedral {Ni(Cp*Ru)3(μ3-H)3(μ-H)3} fragments linked by three bridging hydrogen atoms. Although site exchange of hydrides between the (Cp*RuH4) and {Ni(Cp*Ru)3H6} moieties does not occur on the NMR time scale, incorporation of deuterium into the NiRu3 fragment upon treatment of 2 with 1 atm of D2 establishes that interfragment migration of hydrides does take place. Although reaction of 2 with ethylene results in the replacement of two hydrides in the spiked Ru center by an η2-ethylene ligand, reaction with cyclopentadiene results in the degradation of the pentanuclear skeleton to a tetrahedral cluster, (CpNi)(Cp*Ru)3(μ3-H)3(μ-H)3 (4) (Cp = η5-C5H5), and a mixed-ligand ruthenocene, Cp*CpRu (5).Graphical abstract

Source: Journal of Organometallic Chemistry - December 28, 2018 Category: Chemistry Source Type: research