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, [(η 6 ‐ p ‐cymene)Ru(DDP)Ga(µ‐Cl){Ga(Cl)(N{C 6 H 3 i Pr 2 }) 2 (µ 2 ‐CH 2 C 4 H 5 )}] ( 6 ), is isolated from the reaction of five equivalents of 1 with [(η 6 ‐p ‐cymene)RuCl 2 ] 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 CH 3 group in 1 followed by intramolecular rearrangement. The new compounds are fully characterized by NMR ( 1 H, 13 C) spectroscopy, liquid injection field desorption MS (LIFDI‐MS), and single‐crystal X‐ray diffraction analysis.