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 H2C=CHR to give [Cy2PCH2SiMe2NSiMe2CH 2PCy(C6H8)] Ru, which contains a triply dehydrogenated cyclohexyl ring -allyl bonded to Ru. (PNP-Cy)RuH3 reacts with dihydrofurans to give the heteroatom-stabilized carbene complex (PNP-Cy)RuH[=CO(CH2)3].
