Convenient syntheses of the complexes trans- and cis-[MCl2(HPPh2)4](M = Ru or Os) and cis-[ReCl2(PPh2)-(HPPh2)3], and of salts of the [Rh(HPPh2)4]+, [Ir(CO)(HPPh2)4]+, [RuH(HPPh2)5]+, and trans-[RuH(CO)(HPPh2)4]+ cations are described. The structures and properties of these complexes, including the formation of cis-[OsH2(HPPh2)4], are discussed.