[MN(SPH)CL(3)](2-), [MN(SPH)(3)CL](2-), [ MN-2(SPH)(6)](2-) AND [MN-4(SPH)(6)BR-4](2-) - SYNTHESIS, STRUCTURE AND SELECTED PROPERTIES OF SOME NEW CHALKOGENOLATE COMPLEXES OF DIVALENT MANGANESE

[Me(4)N](2)[Mn(SPh)Cl-3] (1) was obtained by reaction of MnCl2.4H(2)O with one equivalent of NaSPh from methanolic solutions in the presence of [Me(4)N]Cl. Under similar conditions the compound [Et(4)N](2)[Mn(S Ph)(3)Cl] (2) was isolated using [Et(4)N](+) cations. Crystal data: 1: a = 9.425(3), b = 11.903(3), c = 19.073(4) Angstrom, space group P2(1 )cn, Z = 4; 2: a = 14.420(7), b = 13.834(8), c = 17.918(10) Angstrom, beta = 90.69(4)degrees, space group P2(1)/c, Z = 4. The structures wer e refined to R = 0.0839 (1) and 0.0328 (2), respectively. Besides the dianion [Mn(SPh)(3)Cl](2-) (6), crystals of 2 contain traces of [Mn(SP h)(2)Cl-2](2-) (7) distributed over 3.8% of the anion positions. The e xistence of [Mn(SPh)Cl-3](2-) (5), 6 and 7 under similar conditions is interpreted in terms of ligand exchange solution equilibria. Within t hese mononuclear anions, the central metal/sulfur/halide cores show di storted tetrahedral stereochemistries. The reaction of MnCl2 with NaSP h (molar ratio 1:3) in hot mixtures of acetonitrile and DMF leads to [ Mn-2(SPh)(6)](2-) (8), which can be isolated as crystalline [Ph(4)P](2 )[Mn-2(SPh)(6)] (3) with a = 13.383(2), b = 13.565(2), c = 20.438(4) A ngstrom, beta = 106.41(1)degrees, space group P2(1)/c, Z = 2. The fina l refinement converged to R = 0.0380. 8 consists of two edge-sharing M nS4 tetrahedra showing structural similarities with other tetrahedral complexes of the type [M(2)(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/MnB r2/[Et(4)N]Br in hot acetonitrile leads to [Et(4)N](2)[Mn-4(SPh)(6)Br- 4] (4) which crystallizes with a = 14.109(3), b = 27.556(5), c = 16.19 4(4) Angstrom, beta = 95.35(2)degrees, space group P2(1)/n, Z = 4. The structure was refined to R = 0.0583. This compound is also available by reaction of [Et(4)N](2)[Mn(SPh)(4)] with MnBr2 in a molar ratio of 3:5. The anion [Mn-4(SPh)(6)Br-4](2-) (9) contains a central (Mn4S6Br4 ) core which exhibits an adamantane-like structure: A Mn-4 tetrahedron is inscribed into a S-6 octahedron with the S atoms bridging the edge s of the Mn-4 tetrahedron. Terminally bonded Br atoms complete the tet rahedral coordination spheres of the manganese atoms and thus form an outer Br-4 tetrahedron. As a result, the symmetry of the central core comes close to T-d. The observed distortion is attributed to intramole cular repulsions of the organic residues. Selected properties of compo unds 1-4 are reported.