Molybdenum complexes thiophenolates

McDonald JW, Corbin JL, Newton WE. Catalysis by molybdenum complexes. The reaction of diazenes and alcetylenes with thiophenol./norg. Chem. 1976 15 2056-2061. 

The electrochemical reversibility of the M(VI)/M(V) couple for the complexes with sterically hindered ligands contrasts with the reported behavior of the [MoO(SPh)4] complex, which exhibited electrochemical irreversibility for the Mo(V)/Mo(VI) step but a reversible Mo(IV)/ Mo(V) couple. The sterically hindered aromatic substituent groups stabilize the molybdenum(VI) complex and decrease relative to the thiophenol derivative. The molybdenum(VI) species can also be isolated by chemical oxidation. [MoO(PFTP)4] was prepared by chemical redu-tion of [MoO(PFTP)4] . The presence of the electron-withdrawing substituents on the aromatic thiolate increases E ei relative to the thio-phenolate derivative. Evidently the properties of these last complexes are influenced primarily by the electron-withdrawing characteristics of the fluorine substituents rather than by steric factors (33). 

A number of publications detail dimeric molybdenum(V) complexes with three bridging ligands. Thiolate-bridged, [Mo202(p-0)(p-SPh)2(S2CNMe2)2], is prepared upon addition of thiophenol to [Mo02(S2CNMe2)2] in methanol (Eq. 91), and contains a short metal-metal interaction [Mo—Mo 2.649(1) A]... 

---