Synthesis of a New Family of Heterobimetallic Tetranuclear Sulfido Clusters with Mo2Ni2Sx (x = 4 or 5) or Mo3M‘S4 (M‘ = Ru, Ni, Pd) Cores

Treatment of [Cp*Mo(SBu t ) 3 ] ( 1; Cp* = η 5 -C 5 Me 5 ) with [Fc][PF 6 ] (Fc = ferrocene) afforded the cationic sulfido-bridged dinuclear complex [(Cp*MoS)(μ 2 -S) 2 (Cp*Mo)(S 2 Bu t )][PF 6 ] ( 2 ) and the cationic incomplete cubane-type complex [(Cp*Mo) 3 (μ 2 -S) 3 (μ 3 -S)][PF 6 ] ( 3 ) in a ratio of ca. 1:4. The dinuclear complex 2 reacted with [NiCl 2 (PPh 3 ) 2 ] and [Ni(cod) 2 ] (cod = 1,5-cyclooctadiene) to give the heterobimetallic cluster [(Cp*Mo) 2 {Ni(PPh 3 )} 2 (μ 2 -S) 2 (μ 3 -S) 3 ][PF 6 ] ( 4 ) with an unprecedented Mo 2 Ni 2 S 5 core and the edge-linked quadruple cubane-type cluster [(Cp*Mo) 2 Ni 2 (μ 3 -S) 2 (μ 4 -S) 2 ] 4 [PF 6 ] 4 ( 5 ) with four Mo 2 Ni 2 S 4 cores, respectively. On the other hand, the incomplete cubane-type cluster 3 serves as a good precursor to the heterobimetallic cubane-type clusters [(Cp*Mo) 3 (μ 3 -S) 4 M‘L][PF 6 ] (M‘ = Ru, Ni, and Pd).