Me dmpe) are reported. Reaction with GeH4 generates a mixture of cis-and trans-isomers of Ru(PP)2(GeH3)H except for the DuPhos complex which yields the product only in the cis form. In-situ laser photolysis (355 nm) demonstrates that the initial product is the cis-isomer that undergoes thermal isomerization to the trans-isomer. The complex cis-[Ru(dppe)2(GeH3)H] crystallizes selectively, allowing determination of its X-ray structure as a germyl hydride with a long Ru-HGe separation of 2.64(3) Å indicating that no residual interaction between the RuH and Ge is present. DFT calculations are also consistent with full oxidative addition. The structure of cis-[Ru(DuPhos)2(GeH3)H] reveals significant distortion from an octahedral geometry. The major species in the crystal (95%) exhibits a structure with a Ru-HGe distance of 2.42(5) Å suggesting negligible interaction between these centers. DFT calculations of the structure are consistent with the experimental determination. The reactions of Ru(PP)2H2 with diphenylgermane yield cis-[Ru(PP)2(GePh2H)H] exclusively for PP = dmpe and depe, while the cis-isomer is dominant in the case of dppe. A photochemical competition reaction between Ru(dppe)2(H)2 and the two substrates Ph2SiH2 and Ph2GeH2 results in both Si-H and Ge-H oxidative addition activation with a kinetic preference (0.18:1) for the germyl hydride product. Thermal conversion of Ru(dppe)2(SiPh2H)H to Ru(dppe)2(GePh2H)H is observed on heating.