(CuI)3P4S4: Preparation, Structural, and NMR Spectroscopic Characterization of a Copper(I) Halide Adduct with -P4S4

Abstract

CuI) 3 P 4 S 4 is obtained by reaction of stoichiometric amounts of CuI, P, and S in evacuated silica ampoules. The yellow compound consists of monomeric b-P 4 S 4 cage molecules that are separated by hexagonal columns of CuI. (CuI) 3 P 4 S 4 crystallizes isotypic to (CuI) 3 P 4 Se 4 in the hexagonal system, space group P6 3 cm (no. 185) with a 19.082(3), c 6.691(1) ä, V 2109.9(6) ä 3 , and Z 6. Three of the four phosphorus atoms are bonded to copper, whereas no bonds between copper and sulfur are observed. The two crystallographically distinct copper sites are clearly differentiated by 65 Cu magicangle spinning (MAS) NMR spectroscopy. Furthermore, an unequivocal as-signment of the 31 P MAS-NMR spectra is possible on the basis of homo-and heteronuclear dipole ± dipole and scalar interactions. Dipolar coupling to the adjacent quadrupolar spins 63, 65 Cu generates a clear multiplet structure of the peaks attributable to P1 and P2, respectively. Furthermore, the utility of a newly developed two-dimensional NMR technique is illustrated to reveal direct connectivity between P atoms based on ( 31 P ± 31 P) scalar interactions.

Phosphorus Nanorods—Two Allotropic Modifications of a Long‐Known Element

“…Spectra were recorded with rotor-synchronized spin echoes and relaxation delays ranging from 60 to 300 seconds. (CuI) 8 A more detailed investigation of different phosphorus polymorphs, especially red phosphorus from different sources, is in progress to provide more detailed structural information and the influence of the preparation techniques on the molecular structure.…”

“…[6][7][8][9][10][11] Furthermore, polymeric phosphorus strands are readily formed as their copper iodide adducts by treating stoichiometric mixtures of CuX (X = Br, I) with elemental P. Compounds of this kind include two different 1 1 [P 12 ] polymers in (CuI) 8 P 12 [12] and in (CuI) 3 P 12 , [13] Figure 1)-by a low-temperature route. [15] The copper iodide adducts were obtained by a typical high-temperature synthesis and the resulting crystalline materials were subsequently treated with an aqueous solution of potassium cyanide at room temperature.…”

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.…”

Adduct Compounds (MCl5)2(β-P4Ch4) with M = Nb, Ta and Ch = S, Se

“…Compared to other metal halide-containing compounds such as (CuI) 3 (β -P 4 Se 4 ) [6], in (MCl 5 ) 2 (β -P 4 Se 4 ) the bond lengths P(1)-Se (14) and P(2)-Se(24) are shortened, whereas the bonds P(4)-Se (14), P(4)-Se(24) and P(4)-Se(34) are clearly elongated. In the analogous sulfur-containing compounds, only the P-S bond lengths of the apical phosphorus atom change significantly from about 2.10Å in (CuI) 3 (β -P 4 S 4 ) [7] to about 2.13Å in (MCl 5 ) 2 (β -P 4 S 4 ). This certainly has to be attributed to the different coordination of the cages to copper, niobium and tantalum, respectively.…”

“…There is experimental evidence that these molecules either decompose upon heating or even in solution (β -P 4 S 4 ) [2] or polymerize forming chains of catenated molecules (β -P 4 Se 4 ) [3 -5]. However, these β -P 4 Ch 4 phosphorus chalcogenide cages can be found in several quaternary adduct compounds, such as (CuI) 3 (β -P 4 Se 4 ) [6], (CuI) 3 (β -P 4 S 4 ) [7], (CuBr) 3 (β -P 4 Se 4 ) [8], and (NbCl 5 ) 2 (β -P 4 S 4 ) [9], where metal atoms are coordinated to phosphorus atoms of the cages.…”