Crystal structures of 9-[bis(benzylsulfanyl)methyl]anthracene and of cyclo-dodecakis(μ2-phenylmethanethiolato-κ2 S:S)hexapalladium(6 Pd—Pd)–anthracene-9,10-dione (1/1)

The first title compound, C29H24S2, L1, represents an example of an anthracene-based functionalized dithioether, which may be useful as a potential chelating or terminal ligand for coordination chemistry. This dithioacetal L1 crystallizes in the monoclinic space group P21/c. The phenyl rings of the benzyl groups and that of the anthracene unit form dihedral angles of 49.21 (4) and 58.79 (5)° and the crystal structure displays short C–H...π contacts. Surprisingly, when attempting to coordinate L1 to [PdCl2(PhCN)2], instead of the targeted chelate complex [PdCl2(κ2-L1)], a cleavage reaction leads to the formation of the centrosymmetric hexanuclear cyclic cluster of composition [Pd6(μ2-SCH2Ph)12] Pd6, or [Pd6(C7H7S)12]·C14H8O2. This tiara-shaped hexamer crystallizing in the triclinic space group P\overline{1} consists of six approximately square planar Pd(II)S4 centers, which are interconnected through twelve μ2-bridging benzyl thiolate groups. The Pd...Pd contacts range from 3.0892 (2) to 3.1609 (2) Å and can be considered as weakly bonding. The unit cell of Pd6 contains also a co-crystallized anthracene-9,10-dione molecule.

A [Mo2O2S2]-based ring system incorporating tartrate as the bridging ligand: synthesis, structure and catalytic activity of Cs4[Mo2O2(μ-S)2]2(μ4-tart)2 (tart=[C4H2O6]4−)

Treatment of [Mo2S2O2(H2O)6]2+ with racemic tartaric acid (tartH4) in the presence of sodium hydroxide and cesium chloride in aqueous solution led to the isolation of a new tetra-molybdenum ring cluster Cs4[Mo2O2(μ-S)2]2(μ4-tart)2. The cyclic cluster polyanion consists of two dinuclear [Mo2O2(μ-S)2]2+ moieties and two bridging tart4− ligands. The cyclic polyoxothiomolybdate cluster, supported on the mesoporous silica SBA-15, was tested for heterogenerous catalysis in thiophene hydrodesulfurization.

A cyclic mixed-valence MoVI/MoV polyoxothiomolybdate cluster anion stabilized by a [(μ-I){Ag(PPh3)3}2]+ complex cation. Preparation and structure of [(μ-I){Ag(PPh3)3}2]2 [Mo8O8(μ-OH)2(μ-OEt)6(μ-S)8(μ3-O)4{Mo(DMF)2}] · 2EtOH

Treatment of (NMe4)2[Mo2O2S6] with Ag(PPh3)3I in the presence of NaOEt in DMF/EtOH resulted in the formation of a novel MoVI/MoV polyoxothiomolybdate cluster compound [(μ-I){Ag(PPh3)3}2]2[Mo8O8(μ-OH)2 (μ-OEt)6(μ-S)8(μ3-O)4{Mo(DMF)2}] · 2EtOH. The cyclic cluster polyanion consists of an octamer {Mo8O8(μ-OH)2(μ-OEt)6 (μ-S)8(μ3-O)4} that encapsulates a central {MoVI(DMF)2 (μ3-O)4} octahedron.