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(μ-S2), 1, in the presence of irradiation by visible light to yield the new compounds CpMoMn(CO)5[μ-S2CH(CH3)CH(CH3)], 2, CpMoMn(CO)5(μ-S2C12H8), 3, CpMoMn(CO)5[μ-S2CH2CH(CHCH2)], 4, and CpMoMn(CO)5(μ-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 C60 yielded the complex CpMoMn(CO)5(μ-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 1 with elemental sulfur yielded the tetrasulfido complex CpMoMn(CO)5(μ-S4), 7, by addition of an S2 group to the disulfido ligand. All new complexes were characterized by single-crystal X-ray diffraction analysis.