Supramolecular copper halide networks using the coordinative flexibility of the cyclo-P 2S 3 middle deck in (C 5Me 5) 2Mo 2P 2S 3: Phosphorus versus sulfur coordination

Abstract

Reaction of solutions of [ Cp 2 ∗ Mo 2P 2S 3] ( 1; Cp ∗ = η 5-C 5Me 5) in CH 2Cl 2 with solutions of CuHal (Hal = Cl, Br, I) in CH 3CN gave after slow diffusion the novel coordination polymers [ Cp 2 ∗ Mo 2P 2S 3(CuCl) 4] ( 2), [ Cp 2 ∗ Mo 2P 2S 3(CuBr) 3] ( 3) and [ Cp 2 ∗ Mo 2P 2S 3(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-P 2S 3 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-P 2S 3 middle deck is different from that previously found in the starting material 1.