Mixed-Valence Manganese Carbonyl Complexes with Supersilyl Thiolate Ligands: [(OC)4Mn(μ-SSitBu3)2Mn(THF)X] (X = Br, SSitBu3) and Na(THF)6[(OC)3Mn(μ-SSitBu3)3MnSSitBu3]

The manganese carbonyl thiolates [(OC)4Mn(μ-SSitBu3)2Na(THF)2], [(OC)4Mn(μ-SSitBu3)2Mn(THF)Br], [(OC)4Mn(μ-SSitBu3)2Mn(THF)SSitBu3], and Na(THF)6[(OC)3Mn(μ-SSitBu3)3MnSSitBu3] can be prepared from the precursors Na(THF)2SSitBu3 and [Mn(CO)5Br]. When [Mn(CO)5Br] is treated with 1 or 2 equiv of Na(THF)2SSitBu3, the 1:2 substitution product [(OC)4Mn(μ-SSitBu3)2Na(THF)2] (monoclinic, P21/c) is formed quickly. When additional amounts of [Mn(CO)5Br] are present (as in the 1:1 reaction) or are subsequently added to the reaction mixture, the dinuclear Mn(I)Mn(II) complex [(OC)4Mn(μ-SSitBu3)2Mn(THF)Br] (monoclinic, P21/n) can be obtained along with [Mn2(CO)10]. Treatment of [(OC)4Mn(μ-SSitBu3)2Mn(THF)Br] with 1 equiv of Na(THF)2SSitBu3 gives the mixed-valence dinuclear manganese thiolate complex [(OC)4Mn(μ-SSitBu3)2Mn(THF)SSitBu3] (monoclinic, C2/c). Cocrystals of the Mn(I)Mn(II) species Na(THF)6[(OC)3Mn(μ-SSitBu3)3MnSSitBu3] with the trisulfane tBu3Si-SSS-SitBu3 (trigonal, R3̅) are obtained by the reaction of [Mn(CO)5Br] with 2 equiv of Na(THF)2SSitBu3. The complex anion [(OC)3Mn(μ-SSitBu3)3MnSSitBu3]− contains a terminal thiolate ligand with a linear Mn−S−Si unit.