Synthesis and reactivity of germyl complex of Ruthenium(II)

[Display omitted] •Synthesis of optically active half-sandwich chloro, diphosphinite, germyl ruthenium complexes.•X-ray crystal structure of [Ru(GeCl3)(η5-C5Me5)L] (L = (R,R)-(+)-1,2-[bis(diphenyl)phosphanyloxy]-1,2-diphenylethane).•Synthesis of the first bimetallic compounds Ru-GeR3 (R = H, Me) with a chiral phosphinite bidentate ligand. Reaction of [RuCl(η5-C5Me5)L] and [RuCl(η5-C9H7)L] (L = 1,2-[bis(diphenyl) phosphanyloxy]-1,2-diphenylethane) with an excess of GeCl2·dioxane afforded the half-sandwich trichlorogermyl complexes [Ru(GeCl3)(η5-C5Me5)L] (1a) and [Ru(GeCl3)(η5-C9H7)L] (1b). Trihydridogermyl derivatives [Ru(GeH3)(Cp′)L] [Cp′ = η5-C5Me5 (2a), η5-C9H7 (2b)] were obtained by treating 1a and 1b with LiAlH4. Reaction of compound 1a with MeMgBr gave the monomethyl derivative [Ru(GeMeCl2)(η5-C5Me5)L] (3a) while the reaction between the complex 1b and MeMgBr yielded the trimethylgermyl derivative [Ru(GeMe3)(η5-C9H7)L] (3b). All the complexes present optical activity. The complexes were characterized spectroscopically and the X-ray crystal structure of [Ru(GeCl3)(η5-C5Me5)L] (1a) was determined.