A series of cationic dinuclear hydride complexes with bridging thiolato ligands [Cp*MH(mu-SPri)(2)MCp*] [OTf] (4, M = Ru; 6a, M = Rh; 7a, M = Ir; Cp* = eta(5)-C5Me5, OTf = OSO2CS) were synthesized by treatment of the corresponding chloro complexes [Cp*RuCl(mu-SPri)(2)Ru(OH2)Cp*][OTf] (1) or [Cp*M(mu-Cl)(mu-SPri)(2)MCp*] [OTf] (2, M = Rh; 3, M = Ir) with HSiEt3. The dirhodium and diiridium complexes 6 and 7 have been shown to possess a bridging hydride ligand by crystallographic analysis, while the diruthenium complex 4 is proposed to have a terminal hydride ligand that undergoes facile migration between the two ruthenium centers in solution. Complexes 4, 6a, and 7a reacted with nitrosobenzene to give the paramagnetic dinuclear nitrosobenzene complexes [Cp*M(mu-PhNO)(mu-sPr(i))(2)MCp*](+) (M = Ru, Rh, Ir) along with azoxybenzene. The molecular structures of the three nitrosobenzene complexes have been determined by X-ray diffraction study to reveal that in each case nitrosobenzene acts as a mu-eta(1):eta(1)-N,O ligand. Judging from the molecular structures and the ESR spectra, the unpaired electron is considered to be located mainly on the nitrosobenzene ligand, at least in the diruthenium and dirhodium complexes. On the other hand, complex 2 reacted with nitrosobenzene to give the incomplete cubane-type trinuclear cluster [(Cp"Rh)(3)(mu-Cl)(2)(mu(3)-S)(mu-SPri)](+), whose molecular structure has also been determined crystallographically.