Insertion of cyclopentadienylmetal groups into the S-S bond of Mn2(CO)7(μ-S2)

The reaction of Mn-2(CO)(7)(mu-S-2),2, with CpCo(CO)(2) and Cp*Rh(CO)(2) (Cp* = C5Me5) yielded the new complexes CpCoMn2(CO)(6)(mu(3)-S)(2), 3, and Cp*RhMn2(CO)(6)(mu(3)-S)(2), 4, in 79%, and 38% yields, respectively. The reaction of 2 with CpCo(CO)(PPh3) yielded 3, CpCoMn2(CO)(5)(PPh3)(mu(3)-S)(2), 5 (a phosphine derivative of 3), and Mn-2(CO)(6)(PPh3)(mu-S-2), 6 (a phosphine derivative of 2). Compound 5 was also obtained in 88% yield from the reaction of 3 with PPh3. All new products were characterized crystallographically. Compounds 3-5 are structurally similar and consist of a triangular Mn2M cluster with triply bridging sulfido ligands on each side of the Mn2M plane. Compound 6 contains an asymmetrical semibridging carbonyl ligand that is most strongly associated with the phosphine-substituted manganese atom.