Light-promoted addition of alkenes, dienes, C60, and disulfur to the disulfido ligand in the complex CpMoMn(CO)5(μ-S2)

The alkenes, cis-butene, C12H8 (acenaphthylene), and dienes, 1,3-butadiene and cyclopentadiene, were found to add to the mixed-metal disulfido complex CpMoMn(CO)(5)(mu-S-2), 1, in the presence of irradiation by visible light to yield the new compounds CpMoMn(CO)(5)[mu-S(2)GH(CH3)CH(CH3)1,2, CpMoMn(CO)(5)(mu-S2C12H8), 3, CpMoMn(CO)(5)W-S2CH2CH(CH=CH2)] 4, and CpMoMn(CO)5(mu-S2C5H6), 5, by 1,2-insertion of a C-C double bond into the S-S bond of 1. The cis-butene was inserted into the S-S bond with retention of stereochemistry. The reaction of 1 with C-60 yielded the complex CpMoMn(CO)(5)(mu-S2C60), 6, in the presence of room light. A crystallographic study of 6 showed that the C60 was inserted into the S-S bond at one of its 6,6 ring junctions. The reaction of I with elemental sulfur yielded the tetrasulfido complex CpMoMn(CO)(5)(mu-S-4), 7, by addition of an S-2 group to the disulfido ligand. All new complexes were characterized by single-crystal X-ray diffraction analysis.