The reactions of Cp*M(PMe 3 )Cl 2 (M ϭ Rh (1a), Ir (1b)) with (NEt 4 ) 2 [WS 4 ] led to the heterodimetallic sulfido-bridged complexes Cp*M(PMe 3 )[(µ-S) 2 WS 2 ] (M ϭ Rh (2a), Ir (2b)), whereas the dimers [Cp*MCl(µ-Cl)] 2 (M ϭ Rh (4a), Ir (4b)) reacted with (NEt 4 ) 2 [WS 4 ) to give the known trinuclear compounds [Cp*M(Cl)] 2 (µ-WS 4 ) (M ϭ Rh (5a), Ir (5b)). Hydrolysis of the terminal WϭS bonds converts 2a,b into Cp*M(PMe 3 )[(µ-S) 2 WO 2 ] (M ϭ Rh (3a), Ir (3b)). Salts of a heterodimetallic anion, A[CpMo-(I)(NO)(WS 4 )] (6) (A ϩ ϭ NEt 4 ϩ , NPh 4 ϩ ) were obtained by reactions of [CpMo(NO)I 2 ] 2 with tetrathiotungstates, A 2 [WS 4 ]. The