Recrystallization of the solid Cd 10 S 4 (SC 6 H 5 ) 12 from a solution of pyridine and N,N-di-methytformamide (DMF) results in the formation of the cluster Cd 32 S 1 4 (SC 6 H 5 ) 36 -DMF 4 as pale yellow cubes. The structure consists of an 82-atom CdS core that is a roughly spherical piece of the cubic sphalerite lattice -12 angstroms in diameter. The four corners of the lattice are capped by hexagonal wurtzite-like CdS units, which results in an overall tetrahedral cluster ∼ 15 angstroms in diameter. This cluster dissolves intact in tetrahydrofuran where its absorption spectrum reveals a sharp peak at 358 nanometers at room temperature and its emission spectra show a strong broad band at 500 nanometers.

Crystal structure and optical properties of Cd32S14(SC6H5)36-DMF4, a cluster with a 15 angstrom CdS core

A sequence of first row transition metal(II) dithiolates M(SAr*)2 (M = Cr(1), Mn(2), Fe(3), Co(4), Ni(5) and Zn(6); Ar* = C6H3-2,6-(C6H2-2,4,6-Pri3)2) has been synthesized and characterized. Compounds 1−5 were obtained by the reaction of two equiv of LiSAr* with a metal dihalide, whereas 6 was obtained by treatment of ZnMe2 with 2 equiv of HSAr*. They were characterized by spectroscopy, magnetic measurements, and X-ray crystallography. The dithiolates 1, 2, and 4−6 possess linear or nearly linear SMS units with further interactions between M and two ipso carbons from C6H2-2,4,6-Pri3 rings. The iron species 3, however, has a bent geometry, two different Fe−S distances, and an interaction between iron and one ipso carbon of a flanking ring. The secondary M−C interactions vary in strength in the sequence Cr2+ ≈ Fe2+ > Co2+ ≈ Ni2+ > Mn2+ ≈ Zn2+ such that the manganese and zinc compounds have essentially two coordination but the chromium and iron complexes are quasi four and three coordinate, respectively. The...

Synthesis and Characterization of Quasi-Two-Coordinate Transition Metal Dithiolates M(SAr*)2 (M = Cr, Mn, Fe, Co, Ni, Zn; Ar* = C6H3-2,6(C6H2-2,4,6-Pri3)2

The Chemistry of Metal Complexes with Selenolate and Tellurolate Ligands

Two silver(I) complexes, [{Ag(SR)}6][R1SH = 6-(tert-butyldimethylsilyl)pyridine-2-thione 1, R2SH = 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thione 2], have been synthesized by electrochemical oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones. The reaction of equimolar amounts of dppm [bis(diphenylphosphino)methane] with complexes 1 and 2 in dichloromethane resulted in the formation of [Ag4Cl4(dppm)2]3 and the elimination of RSCH2SR. Single-crystal X-ray analyses were performed for compounds 1, 3 and R2SCH2SR2.

Electrochemical synthesis and crystal structure of silver(I) complexes with some heterocyclic thiones

The chemistry of inorganic and organometallic compounds with adamantane-like structures

The reactions of 1:1:1 molar ratio mixtures of NaSPh/MnCl 2 /Et 4 NBr and NaSPh/CoCl 2 /Et 4 NCl in methanol afford the compounds [Et 4 N] 4 °Mn(SPh) 3 Br][Mn(SPh) 3 Cl] (1) and [Et 4 N] 2 °Co 4 (SPh) 6 Cl 4 ].MeCN (2), respectively, with the following crystal data: space group P2 1 /c for 1, and space group P2 1 /c for 2.

[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

[Mn4Te4(SC3H7)4]4− and [Mn4Te4(SeC3H7)4]4−: Novel Heterocubane Clusters of Manganese

Synthesis, structure and properties of di- and tetranuclear manganese(II) chalcogenolate complexes [Mn2(SC3H7)6]2−, [Mn2(SCH3)6]2−, [Mn2(SeC3H7)6]2−, [Mn4(SC3H7)6Cl4]2− and [Mn4(SeC3H7)6Br4]2−

Novel metal thiolates: [Mn2(SC6H3{SiMe3}2)4(C4H8O)], a binuclear manganese thiolate complex with tetrahedral and trigonal-planar metal coordination

[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 Td. The observed distortion is attributed to intramolecular repulsions of the organic residues. Selected properties of compounds 1-4 are reported.

[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

Hans-Oscar Stephan

Papers

[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

[Mn4Te4(SC3H7)4]4− and [Mn4Te4(SeC3H7)4]4−: Novel Heterocubane Clusters of Manganese

Synthesis, structure and properties of di- and tetranuclear manganese(II) chalcogenolate complexes [Mn2(SC3H7)6]2−, [Mn2(SCH3)6]2−, [Mn2(SeC3H7)6]2−, [Mn4(SC3H7)6Cl4]2− and [Mn4(SeC3H7)6Br4]2−

Novel metal thiolates: [Mn2(SC6H3{SiMe3}2)4(C4H8O)], a binuclear manganese thiolate complex with tetrahedral and trigonal-planar metal coordination