Light-promoted addition of alkenes, dienes, C ₆₀, and disulfur to the disulfido ligand in the complex CpMoMn(CO) ₅(μ-S ₂)

The alkenes, cis-butene, C ₁₂H ₈ (acenaphthylene), and dienes, 1,3-butadiene and cyclopentadiene, were found to add to the mixed-metal disulfido complex CpMoMn(CO) ₅(μ-S ₂), 1, in the presence of irradiation by visible light to yield the new compounds CpMoMn(CO) ₅[μS ₂CH(CH ₃)CH(CH ₃)], 2, CpMoMn(CO) ₅(μ-S ₂H ₃), 3, CpMoMn(CO) ₅[μ-S ₂CH ₂CH(CH=CH ₂)], 4, and CpMoMn(CO) ₅(μ-S ₂C ₅H ₆), 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(μ-S ₂C ₆₀), 6, in the presence of room light. A crystallographic study of 6 showed that the C ₆₀ was inserted into the S-S bond at one of its 6,6 ring junctions. The reaction of 1 with elemental sulfur yielded the tetrasulfido complex CpMoMn(CO) ₅(μ-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.