Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P4Se3 and CuX (X=Cl, Br, I)

Biegerl, Andreas; Gröger, Christian; Kalbitzer, Hans Robert; Pfitzner, Arno; Wächter, Joachim; Weihrich, Richard; Zabel, Manfred

doi:10.1016/j.jssc.2011.05.011

Cited by 12 publications

(6 citation statements)

References 24 publications

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“…The existence of two phosphorus resonances may be explained by a different orientation of the cage molecules in the crystal. This phenomenon was first described for β-P 4 S 3 and was also found for P 4 Se 3 . Because of the extremely low solubility of PAs 3 S 3 in, e.g., toluene, CH 2 Cl 2 , and THF we investigated formation of an adduct with W(CO) 5 .…”

Section: Resultssupporting

confidence: 55%

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PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

2011

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First examples of the coordination chemistry of the PAs(3)S(3) cage were obtained from solutions of PAs(3)S(3)·W(CO)(5) (1) in CH(2)Cl(2) or CH(2)Cl(2)/toluene and CuX (X = Cl, Br, I) in MeCN through interdiffusion techniques. Crystals of [Cu(PAs(3)S(3))(4)]X (2, X = Cl; 3, X = Br) and [(Cu(2)I)(PAs(3)S(3))(3)]I (4) were obtained and characterized by Raman spectroscopy (2) and single-crystal X-ray crystallography. The solid-state structures reveal an unexpected coordination versatility of the PAs(3)S(3) ligand: apical phosphorus and bridging sulfur atoms interact with copper, while As···X interactions determine the dimensionality of the frameworks. The structures of 2 and 3 contain tetrahedral [(PAs(3)S(3))(4)Cu](+) cations as secondary building units (SBUs), which are arranged by interactions with Cl(-) or Br(-) anions into two- and three-dimensional substructures. These interpenetrate into a (2D + 3D) polycatenane. Compound 4 is built up by a one-dimensional [(Cu(2)I)(PAs(3)S(3))(3)](n)(n+) ribbon with PAs(3)S(3) cages as P,S-linkers. The As atoms of the exo PAs(3)S(4) linkers interact with iodide counterions (3.35 < d(As-I) < 3.59 Å). The resulting two-dimensional layer is organized by weak As···I interactions (d(As-I = 3.87 Å) into a 3D network.

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Section: Resultssupporting

confidence: 55%

“…This phenomenon was first described for β-P 4 S 3 12 and was also found for P 4 Se 3 . 13 Because of the extremely low solubility of PAs 3 S 3 in, e.g., toluene, CH 2 Cl 2 , and THF we investigated formation of an adduct with W(CO) 5 . In analogy to the chemistry of As 4 S 3 , such an adduct should be much more soluble.…”

Section: ' Introductionmentioning

confidence: 99%

PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

2011

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“…Single crystals of MoOCl 3 (THF) 2 were obtained during our explorative investigations of the reactivity of phosphorus chalcogenide cage molecules towards transition metal halides [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. We stirred 0.1 g Mo 2 Cl 10 (0.4 mmol, 1 eqiv.…”

Section: Methodsmentioning

confidence: 99%

Structural characterization of MoOCl3(THF)2, the pre-reagent for Kauffmann olefination reactions

2017

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Single crystals of molybdenum-oxy-di-tetrahydrofuran-trichloride were obtained by the reaction of Mo 2 Cl 10 , tetrahydrofuran, sulfur, and P 4 S 3 in carbon disulfide after layering the solution with n-hexane. Single crystal structure determination at T = 123 K reveals that MoOCl 3 (THF) 2 crystalizes in the orthorhombic space group P2 1 2 1 2 1 with the lattice constants a = 7.8620(9) Å , b = 12.302(1) Å , c = 14.043(2) Å , V = 1304.10(3) Å 3 , and Z = 4. EPR experiments on the solid compound showed a g value of 1.94 at 347.46 mT, which accords to a Mo(V) species. The electronic structure of the title compound was investigated with DFT methods.

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“…[11] Recent developments focus on the construction of organicinorganic hybrid materials from bifunctional P,N or S,N ligands. [12,13] Inorganic polymers of a completely different nature have been developed using the multifunctional P,Q building block P 4 Q 3 (Q = S, [14,15] Se [16] ). The combination of organic and inorganic donors as cross-linking ligands with copper halide aggregates has not yet been explored.…”

Section: Introductionmentioning

confidence: 99%

P₄S₃ and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers

et al. 2011

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The synthesis and characterization of hybrid polymers combining organic P,PЈ (dppe) or N,NЈ (pyrazine) ligands and inorganic donors (P 4 S 3 ) as cross-linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P 4 S 3 , PEt 3 , and CuX (X = Cl, Br, I) was studied. According to X-ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt 3 ) 2 (P 4 S 3 )] (1-3) were formed, in which P 4 S 3 coordinates through the apical phosphorus atom. Layering a mixture of P 4 S 3 , Ph 2 PCH 2 CH 2 PPh 2 (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu 2 Cl 2 ) 2 -(μ-dppe) 2 clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D-[CuI(P 4 S 3 )(dppe)] (7), which is built up of alternating trans-(Cu 2 I 2 )(P 4 S 3 ) 2 units and dppe linkers. Hybrid polymers 2D-[CuX(P 4 S 3 )(dppe)] [X = Br (8), I (9)] are formed if CH 2 Cl 2 is used instead of toluene. The 2D

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Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P4Se3 and CuX (X=Cl, Br, I)

Cited by 12 publications

References 24 publications

PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

Structural characterization of MoOCl3(THF)2, the pre-reagent for Kauffmann olefination reactions

P₄S₃ and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers

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Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P4Se3 and CuX (X=Cl, Br, I)

Cited by 12 publications

References 24 publications

PAs3S3 Cage as a New Building Block in Copper Halide Coordination Polymers

PAs3S3 Cage as a New Building Block in Copper Halide Coordination Polymers

Structural characterization of MoOCl3(THF)2, the pre-reagent for Kauffmann olefination reactions

P4S3 and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers

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PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

PAs₃S₃ Cage as a New Building Block in Copper Halide Coordination Polymers

P₄S₃ and P,P′ or N,N′ Donors as Competitive Building Blocks in Copper(I) Coordination Polymers