[Mn(SPh)Cl₃]^2-, [Mn(SPh)₃Cl]^2-, [Mn₂(SPh)₆]^2- und [Mn₄(SPh)₆Br₄]^2–: Synthese, Struktur und ausgewählte Eigenschaften einiger neuer Chalkogenolatkomplexe des zweiwertigen Mangans / [Mn(SPh)Cl₃]^2-, [Mn(SPh)₃Cl]^2-, [Mn₂(SPh)₆]^2- und [Mn₄(SPh)₆Br₄]^2-: Synthesis, Structure and Selected Properties of Some New Chalkogenolate Complexes of Divalent Manganese

[Me₄N]₂[Mn(SPh)Cl₃] (1) was obtained by reaction of MnCl₂·4H₂O with one equivalent of NaSPh from methanolic solutions in the presence of [Me₄N]Cl. Under similar conditions the compound [Et₄N]₂[Mn(SPh)₃Cl] (2) waso isolated using [Et₄N]⁺ cations. Crystal data: 1: a = 9.425(3), b = 11.903(3)t c -19.073(4) Å, space group P 2₁cn, Z = 4; 2: a = 14.420(7), b = 13.834(8), c = 17.918(10) Å, β = 90.69(4)°, space group P2₁/c, Z = 4. The structures were refined to R = 0.0839 (1) and 0.0328 (2), respectively. Besides the dianion [Mn(SPh)₃Cl]^2- (6), crystals of 2 contain traces of [Mn(SPh)₂Cl₂]^2- (7) distributed over 3.8% of the anion positions. The existence of [Mn(SPh)Cl₃]^2- (5), 6 and 7 under similar conditions is interpreted in terms of ligand exchange solution equilibria. Within these mononuclear anions, the central metal/sulfur/halide cores show distorted tetrahedral stereochemistries. The reaction of MnCl₂ with NaSPh (molar ratio 1:3) in hot mixtures of acetonitrile and DMF leads to [Mn₂(SPh)₆]^2- (8), which can be isolated as crystalline [Ph₄P]₂[Mn₂(SPh)₆] (3) with a = 13.383(2), b = 13.565(2), c = 20.438(4) Å, β = 106.41(1)°, space group P2₁/c, Z = 2. The final refinement converged to R = 0.0380. 8 consists of two edge-sharing MnS₄ tetrahedra showing structural similarities with other tetrahedral complexes of the type [M₂(SR)₆]^2-. According to magnetochemical studies, the manganese atoms are antiferromagnetically coupled with J=-18.6(2) cm^-1. Reaction of 3:2:1 molar ratio mixtures of NaSPh/MnBr₂/[Et₄N]Br in hot acetonitrile leads to [Et₄N]₂[Mn₄(SPh)₆Br₄] (4) which crystallizes with a = 14.109(3), b = 27.556(5), c = 16.194(4) Å, β = 95.35(2)°, space group P 2₁/n, Z=4. The structure was refined to R = 0.0583. This compound is also available by reaction of [Et₄N]₂[Mn(SPh)₄] with MnBr₂ in a molar ratio of 3:5. The anion [Mn₄(SPh)₆Br₄]^2- (9) contains a central {Mn₄S₆Br₄} core which exhibits an adamantane-like structure: A Mn₄ tetrahedron is inscribed into a S₆ octahedron with the S atoms bridging the edges of the Mn₄ tetrahedron. Terminally bonded Br atoms complete the tetrahedral coordination spheres of the manganese atoms and thus form an outer Br₄ tetrahedron. As a result, the symmetry of the central core comes close to T_d. The observed distortion is attributed to intramolecular repulsions of the organic residues. Selected properties of compounds 1-4 are reported.