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}) 2(μ2-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. The reactions of low-valent six-membered β-diketiminate-gallium(I), Ga(DDP) [DPP = HC(CMeNC 6H3-2,6-iPr2)2], with [Cp*Ru(μ-H)2]2 (Cp* = pentamethylcyclopentadiene) and [(η6-p-cymene)RuCl 2]2 lead to [(Cp*Ru)2(μ-H) 2{μ-Ga(DDP)}] (3) and[(η6-p-cymene)Ru(DDP)Ga(μ- Cl){Ga(Cl)(N{C6H3iPr2})2(μ 2-CH2C4H5)}] (6), respectively. Compound 6 is a cycloruthenated product formed by an intramolecular C-H bond cleavage reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.