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

Baláȥs, Gábor; Biegerl, Andreas; Gröger, Christian; Wächter, Joachim; Weihrich, Richard; Zabel, Manfred

doi:10.1002/ejic.200901108

Cited by 11 publications

(5 citation statements)

References 45 publications

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“…The interaction of the As 3 basis with the Cl – anion is held responsible for this splitting (see below), although it is difficult to assign the vibrations. A similar influence of copper coordination on P 4 S 3 Raman frequencies has been studied recently …”

Section: Resultsmentioning

confidence: 71%

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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: Resultsmentioning

confidence: 71%

“…The 31 P NMR spectrum in C 6 D 6 shows a singlet at δ = 115.9 ppm. The observed 1 J P,W coupling of 300 Hz is stronger than that in P 4 S 3 ·W(CO) 5 (126 Hz) . The 31 P MAS NMR spectrum contains one signal at δ = 113.0 ppm and weak resonances at δ = 109 and −64.3 ppm indicating impurities of still unknown nature.…”

Section: Resultsmentioning

confidence: 79%

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

2011

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“…The first complex Mo(CO) 5 (P 4 S 3 ) was already reported in 1974 . In the meantime many other complexes of P 4 S 3 have been synthesized using various metals such as Cu, W, Ni, Pd, Ru, Rh, Fe and even BX 3 (Figure ) , , . The homoleptic complexes Ag(P 4 S 3 ) 2 [Al(OR F ) 4 ] and Ag(P 4 S 3 ) 3 [Al(OR F ) 4 ] featured the previously unknown sulfur coordination modes of this ligand , .…”

Section: Introductionmentioning

confidence: 93%

Homoleptic Silver Complexes of the Cages P₄Se₃ and As₄S₃

et al. 2018

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By reacting P 4 Se 3 and As 4 S 3 with Ag[Al(OR F ) 4 ] {-R F = -C(CF 3 ) 3 or -hfip [= -C(H)(CF 3 ) 2 ]} in suitable solvents, (5) were synthesized and characterized by SC-XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P 4 Se 3 forms an isolable complex yielding 1 featuring a [Ag 2 (P 4 Se 3 ) 2 ] 2+ core capped by anions acting as the first example of P 4 Se 3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF 3 ) 3 } 4 ] -, the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho-difluorobenzene (o-dfb), respectively. Complex 2 shows isolated [Ag 2 (P 4 Se 3 ) 4 - [a] Computational Details: All computations were performed by using the program package TURBOMOLE 7.1. [38] All investigated molecular structures were optimized using the functionals BP86 [39] (with RI approximation [40] ) and together with the basis sets def-SV(P). [41] A fine integration grid (m4) and the default SCF convergence criteria (10 -6 a.u.) were used. The vibrational frequencies of all assessed species were computed with the implemented module AOFORCE [42] and checked for minima (no imaginary frequencies).Preparation of P 4 Se 3 : P 4 Se 3 was obtained by heating stoichiometric amounts of grey selenium and white phosphorus in tetraline followed by extraction and recrystallization in CS 2 , following the literature procedure. [43] FT-Raman: ν = 135 (vw), 214 (m), 317 (sh), 324 (vw), 346 (sh), 365 (vs), 370 (sh), 405 (vw), 484 (w) cm -1 . NMR: 31 P NMR (122 MHz, CS 2 , r.t.): δ = -104.6 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 37.4 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. 77 Se (57 MHz, CS 2 , r.t.): δ = 763.3 (m, P 4 77 SeSe 2 ) ppm. 31 P NMR (162 MHz, CD 2 Cl 2 , r.t.): δ = -114.1 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 30.5 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. 31 P NMR (162 MHz, SO 2 , r.t.): δ = -113.7 [d, 3 P basal , 2 J(P basal , P apical ) = 72 Hz], 29.6 [q, 1 P apical , 2 J(P basal , P apical ) = 72 Hz] ppm. Mass Spectra: (ASAP, Source Voltage 25 V, Source Offset 25 V, Temperature 400°C, positive): m/z = 173 [P 3 80 Se] + , 365 [HP 4 80 Se 3 ] + .Preparation of As 4 S 3 : As 4 S 3 was obtained by melting stoichiometric amount of the elements for five days at 420°C, followed by Soxhlet-extraction with toluene. FT-Raman: ν = 145 (vw), 172 (w), 186 (m), 207 (m), 217 (m), 230 (sh), 273 (vs), 338 (sh), 359 (m), 375 (vw) cm -1 . Mass Spectra: (ASAP, Source Voltage 25 V, Source Offset 25 V, Temperature 400°C, positive): m/z = 257 [As 3 32 S] + , 289 [As 3 32 S 2 ] + , 321 [As 3 32 S 3 ] + , 396 [As 4 32 S 3 ] + , 397 [HAs 4 32 S 3 ] + , 428 [As 4 32 S 4 ] + , 429 [HAs 4 32 S 4 ] + .

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“…26 Since its synthesis in 2002 a wide area of chemistry has been developed including an abundance of new single source precursors for telluride based materials. The homoleptic cadmium complex Cd[(TeP i Pr 2 ) 2 N] 2 (35) was utilized as the first single source precursor to generate CdTe nano-rods or -pods from the vapour phase which were deposited on Au/Si islands. 27 The tin and lead complexes (36) of the [(TeP i Pr 2 ) 2 N] and [TeP i Pr 2 -NP i Pr 2 Se] ligands were prepared by metathesis reaction of the metal halides and alkali-metal salts of the ligand.…”

Section: Radical Systemsmentioning

confidence: 99%

“…34 The reaction of P 4 S 3 ÁW(CO) 5 with CuI or CuBr produces organometallic-inorganic hybrid coordination polymers. 35,36 The bis(chalcogenophosphate) ligands (49) were prepared by chalcogen insertion into the Li-P bond. 37 A tetrahalogenated diphosphadithiatetrazocine [50; 1,5-Cl 2 P(NSN)PCl 2 ] was prepared by the cyclization of SCl 2 and SO 2 Cl 2 with Cl 2 P(NSiMe 3 )N(SiMe 3 ) 2 .…”

Section: Radical Systemsmentioning

confidence: 99%

Oxygen, sulfur, selenium, tellurium and polonium

Martin

Ragogna

2011

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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

Cited by 11 publications

References 45 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

Homoleptic Silver Complexes of the Cages P₄Se₃ and As₄S₃

Oxygen, sulfur, selenium, tellurium and polonium

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

Cited by 11 publications

References 45 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

Homoleptic Silver Complexes of the Cages P4Se3 and As4S3

Oxygen, sulfur, selenium, tellurium and polonium

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

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

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

Homoleptic Silver Complexes of the Cages P₄Se₃ and As₄S₃