Reactions of the bis(hydrosulfido) complexes [Cp*Rh(SH)(2)(PMe3)] (1a; Cp* = eta(5)-C5Me5) with [CpTiCl3] (Cp = eta(5)-C5H5) and [TiCl4(thf)(2)] in the presence of triethylamine led to the formation of the sulfido-bridged titanium-rhodium complexes [Cp*Rh(PMe3)(mu(2)-S)(2)TiClCp] (2a) and [Cp*Rh(PMe3)(mu(2)-S)(2)TiCl2] (3a), respectively. Complex 3a and its iridium analogue 3b were further converted into the bis(acetylacetonato) complexes [Cp*M(PMe3)(mu(2)-S)(2)Ti(acac)(2)] (4a, M = Rh; 4b, M = Ir) upon treatment with acetylacetone. The hydrosulfido complexes 1a and [Cp*Ir(SH)(2)(PMe3)] (1b) also reacted with [VCl3(thf)(3)] and [Mo(CO)(4)(nbd)] (nbd = 2,5-norbornadiene) to afford the cationic sulfido-bridged VM2 complexes [{Cp*M(PMe3)(mu(2)-S)(2)}(2)V](+) (5a(+), M = Rh; 5b(+), M = Ir) and the hydrosulfido-bridged MoM complexes [Cp*M(PMe3)(mu(2)-SH)(2)Mo(CO)(4)] (6a, M = Rh; 6b, M = Ir), respectively.