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N-Heterocyclic Gallylene Supported Organoruthenium Derivatives – Synthesis, Structure, and C–H Bond Cleavage



The reaction of the low-valent and sterically bulky gallium(I) compound Ga(DDP) (1, DDP = 2-diisopropylphenylamino-4-diisopropylimino-2-pentene) with an equimolar amount of the tetrahydrido-bridged complex [Cp*Ru(μ-H)2]2 (2, Cp* = pentamethylcyclopentadiene) in toluene at 70 °C results in the Ga(DDP)-bridged diruthenium complex [(Cp*Ru)2(μ-H)2{μ-Ga(DDP)}] (3). Furthermore, a cyclometallated ruthenium complex, [(η6-p-cymene)Ru(DDP)Ga(µ-Cl){Ga(Cl)(N{C6H3iPr2})22-CH2C4H5)}] (6), is isolated from the reaction of five equivalents of 1 with [(η6-p-cymene)RuCl2]2 (4) in n-hexane at reflux. The red crystalline compound 3 contains a [Cp*Ru] dimer bridged by Ga(DDP) and two hydrido ligands with a Ga–Ru–Ru triangle. Compound 6 is obtained by a C–H bond cleavage process of a CH3 group in 1 followed by intramolecular rearrangement. The new compounds are fully characterized by NMR (1H, 13C) spectroscopy, liquid injection field desorption MS (LIFDI-MS), and single-crystal X-ray diffraction analysis.