The Unexpected Versatility of P₄S₃ as a Building Block in Polymeric Copper Halide Networks: 2,3‐P, 1,2,3‐P and all‐P Coordination

Abstract

Layering solutions of P(4)S(3) in CH(2)Cl(2) with solutions of CuCl or CuI in CH(3)CN gives the coordination polymers (P(4)S(3))(3)(CuCl)(7) (1), (P(4)S(3))(2)(CuCl)(3) (2), (P(4)S(3))(CuI) (3) and (P(4)S(3))(CuI)(3) (4), respectively, after slow diffusion. The yellow compounds were characterised by elemental analysis, (31)P magic-angle spinning (MAS) NMR spectroscopy and single-crystal X-ray crystallography. The solid-state structures demonstrate the unexpected ligand versatility of the P(4)S(3) molecule, which interacts through two, three, or even all of the phosphorus atoms with copper according to the nature of the copper halide. Compound 1 has a three-dimensional network in which linear and cylindrical infinite CuCl subunits coexist with diatomic CuCl building blocks. For the first time, all four P atoms of the P(4)S(3) cage are involved in coordination with metal atoms. The 3D structure of 2 contains stacks of P(4)S(3) that are interconnected by slightly undulated and planar [CuCl](n) ribbons. Compound 3 is a one-dimensional polymer composed of alternating (CuI)(2) rings and P(4)S(3) bridges. The structure of 4 consists of undulated [CuI](n) layers in which the P(4)S(3) cage functions as a bridge within the layer, as well as a spacer between the layers. The (31)P MAS NMR spectra obtained are in good agreement with the solid-state structures obtained crystallographically. Thus, analytically pure 3 and 4 show singlet peaks that correspond to uncoordinated P and quartets owing to coupling with (63)Cu and (65)Cu, respectively, whereas that of 1 contains quartets according to all-P coordination. The spectrum of 2 was obtained from a sample that still contained 40 % of 1.

Ring‐shaped [(TiCl2)(1,3‐P2S8)]2 Molecules Containing Uncommon [P2S8]2– Anions

“…These have different phosphorus and sulfur atoms within the cages which can act as possible coordination sites, and α-P 4 S 7 and P 4 S 10 furthermore exhibit terminal sulfur atoms as possible coordination sites. These cages should be able to act as Lewis-bases similar as found for other metal halides (see for example [7][8][9][10]). Herein we present [(TiCl 2 )(1,3-P 2 S 8 )] 2 which was obtained en route from TiCl 4 and P 4 S 10 in CS 2 at room temperature.…”

Novel Coordination Modes for E4S3 Cage Molecules (E = P, As) in Unprecedented Quaternary As4S3(CuCl)n (n = 1,2) Solid‐State Phases

“…[3] Recently, coordination of all phosphorus atoms of the cage has been realized in the quaternary solid-state compound (P 4 S 3 ) 3 (CuCl) 7 , which is the result of the interaction of solutions of P 4 S 3 and CuCl in different solvents by diffusion techniques. [4] The coordination chemistry of the heavier homologue of P 4 S 3 , As 4 S 3 , might be considered as much more frustrating. Only a few reactions of the As 4 S 3 cage with transition-metal complexes have been described, [5] very likely because of the poor solubility of the cage in organic solvents.…”

Theoretical and Spectroscopic Investigation of Coordination Compounds from P4S3, Copper(I) Iodide and W(CO)5

“…Up to four cage phosphorus atoms are involved as coordination sites, but not sulfur. [4] The nature of the CuHal substructures depends on the employed halogen (Cl -or I -). The coordination behavior of CuBr is not as straightforward and will be reported elsewhere.…”