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Abstract: Cage molecules with mixed group 15 (E=P, As) and group 16 elements (Q=S, Se) are versatile ligands in coordination chemistry. The introduction of solid-state techniques allows one to extend the coordination flexibility of the cage molecules and to realize new coordination modes. The use of P4S3 or As4S3 as building blocks in copper(I) halide networks has initiated a new kind of “soft” solid-state chemistry, in which solutions of binary inorganic cage molecules are transferred into one-, two- or three-dimensional polymers. This strategy has been stimulated by the existence of competitive phosphorus, arsenic and sulfur coordination sites in the cage molecules. [Copyright &y& Elsevier]

The coordination behavior of [(Cp*Mo)2As2S3] (3) (Cp* = C5Me5) toward Cu(I) halides was investigated. One dimensional polymers of the general formula [(Cp*Mo)2As2S3(CuHal)2]n (Hal = CI, 4; Br, 5) and an oligomer of composition [{(Cp*Mo)2As2S3}3(Cul)7] (6) formed upon the reaction of 3 with the corresponding copper halide. All of the compounds were characterized by ESI-MS, elemental analysis, and single-crystal X-ray crystallography. The solid-state structures of 4 and 5 are isostructural and contain 1D S-shaped chains. This peculiar folding is achieved by alternating planar and folded Cu2Hal2 rings linked together by the central monosulfide bridge of the middle deck of the organometallic unit. The structure of 6 is characterized by a novel [Cul]7 aggregate, which forms a very flat Cu6l3S3 bowl along with three integrated peripheral [(Cp*Mo)2As2S3] building blocks. In contrast to earlier findings, the middle deck of the organometallic units consists in all structures of two trapezoidal AsS dumbbells and one monosulfide ligand. [ABSTRACT FROM AUTHOR]

Abstract: The formation of coordination polymers (CuCl)P4Se3 (1), (CuBr)3(P4Se3)2 (2), (CuI)3(P4Se3)2 (3) and (CuI)P4Se3 (4), from solutions of copper(I) halides and P4Se3 by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state 31P MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480cm−1. The structure of 1 consists of a 2D network of castellated [CuCl] n chains and bidentate P4Se3 molecules. The 3D network of 2 comprises [CuBr] n chains, which are linked by tridentate P4Se3 molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI)2 rings and castellated [CuI] n chains, which are linked by tridentate P4Se3 molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230°C gives (CuCl)3(P4Se3)2 (5), which is isostructural with 2. The thermal conversion of (CuI)3P4S3, which was studied for comparison gave at 371°C (CuI)3P4S4, Cu3PS4 and small amounts of Cu6PS5I. [Copyright &y& Elsevier]

Abstract: Reaction of solutions of [Mo2P2S3] (1; =η5-C5Me5) in CH2Cl2 with solutions of CuHal (Hal=Cl, Br, I) in CH3CN gave after slow diffusion the novel coordination polymers [Mo2P2S3(CuCl)4] (2), [Mo2P2S3(CuBr)3] (3) and [Mo2P2S3(CuI)3] (4). The products were characterized by elemental analysis, 31P magic angle spinning (MAS) NMR spectroscopy and single-crystal X-ray crystallography. The solid-state structures of 2 and 3 are composed of two-dimensional polymeric networks, whereas that of 4 contains parallel stacks of one-dimensional ribbons. In all cases the planar cyclo-P2S3 middle deck of the organometallic building block 1 provides one or two P atoms of the PS dumbbells along with the singly bridging sulfur atom as coordination sites for the various copper halide subunits. The assignment of P atoms follows from the correlation of 31P MAS NMR spectra with X-ray crystallographic data. In all compounds the distribution of main group atoms in the cyclo-P2S3 middle deck is different from that previously found in the starting material 1. [Copyright &y& Elsevier]