A disulfide-bridged manganese carbonyl anion: Synthesis, structure and reactivity of

The reduction of Mn₂(CO)₇(μ-S₂), (1) with sodium amalgam in THF provided the new monoanion [Mn₃(CO)₁₀(μ₃-S₂) ₂]^-, (3) isolated in low yield as the [Ph₃PMe] salt. The reaction of Mn₄(CO)₁₅(μ₃-S₂) (μ₄-S₂), (2) with [Ph₃PMe]I provided the same salt [Ph₃PMe] [3] in a good yield, 68%. Anion 3 reacts [CpFe(CO)₂ (acetone)]BF₄ to yield the neutral mixed metal complex CpFeMn₃(CO)₁₂(μ₃-S₂) (μ₄-S₂), (4). The structures of [Ph₃ PMe] [3] and 4 were determined by single crystal X-ray diffraction analyses. The core of the structure of 3 consists of two [Mn(CO)₃] groups bridged by two disulfido ligands in a μ₂-≤^h2 fashion with an additional [Mn(CO)₄] group that bridges the two disulfido ligands. The CpFe(CO)₂ group in 4 is bonded to a sulfur atom of one of the two disulfido ligands of the anionic grouping of 3.