The chemistry of the ligand (R₂PCH₂SiMe₂)₂N⁻ (R = cyclohexyl and ^tBu), “PNP-R”, on ruthenium is developed, including RuH(PNP-Cy)(PPh₃) and (HPNP-R)RuH₃Cl. The latter contains a protonated nitrogen (i.e., amine as a donor to Ru) and one H₂ ligand (X-ray structure for R = ^tBu). This compound can be dehydrohalogenated to give (PNP-Cy)RuH₃, which undergoes H/D exchange of D₂ into its cyclohexyl rings, and is itself dehydrogenated by excess H₂CCHR to give [Cy₂PCH₂SiMe₂NSiMe₂CH₂PCy(C₆H₈)] Ru, which contains a triply dehydrogenated cyclohexyl ring π-allyl bonded to Ru. (PNP-Cy)RuH₃ reacts with dihydrofurans to give the heteroatom-stabilized carbene complex (PNP-Cy)RuH[CO(CH₂)₃].