Syntheses, properties, crystal and molecular structure of a novel neutral pentanuclear copper(I) iodide species. Copper(I) complexes with tetraethylthiuram monosulfide ‡

Victoriano, Luis I.; Garland, Marı́a Teresa; Vega, Andrés; López, César A.

doi:10.1039/a709210e

Cited by 14 publications

(4 citation statements)

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“…The structure of cluster 7 featured both a chelate Et-FerroTANE [bite angle = 112.5(3)°] and two bis(phosphetanes) bridging two coppers, with an unusual Cu 5 I 5 core (Figure ). As with Me-FerroLANE in 5 , bridging coordination of Et-FerroTANE had not been observed earlier. For the three different types of bridging iodides in 7 , slightly longer Cu–I bonds were generally observed with larger iodide coordination numbers [for μ 4 -I3, Cu2–I = 2.769(2) Å and Cu3–I = 2.740 Å; for μ 3 -I2, Cu1–I = 2.675(2) Å, Cu2–I = 2.680(3) Å, and Cu3–I = 2.650(2) Å; for μ 2 -I1, Cu2–I = 2.660(3) Å and Cu3–I = 2.669(2) Å].…”

Section: Resultsmentioning

confidence: 60%

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

et al. 2017

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For investigation of structure-property relationships in copper phosphine halide complexes, treatment of copper(I) halides with chiral bis(phosphines) gave dinuclear [Cu((R,R)-i-Pr-DuPhos)(μ-X)] [X = I (1), Br (2), Cl (3)], [Cu(μ-((R,R)-Me-FerroLANE)(μ-I)] (5), and [Cu((S,S)-Et-FerroTANE)(I)] (6), pentanuclear cluster CuI((S,S)-Et-FerroTANE) (7), and the monomeric Josiphos complexes Cu((R,S)-CyPF-t-Bu)(I) (8) and Cu((R,S)-PPF-t-Bu)(I) (9); 1-3, 5, and 7-9 were structurally characterized by X-ray crystallography. Treatment of iodide 1 with AgF gave [Cu((R,R)-i-Pr-DuPhos)(μ-F)] (4). DuPhos complexes 1-4 emitted yellow-green light upon UV irradiation at room temperature in the solid state. This process was studied by low-temperature emission spectroscopy and density functional theory (DFT) calculations, which assigned the luminescence to (M + X)LCT (CuX to DuPhos aryl) excited states. Including Grimme's dispersion corrections in the DFT calculations (B3LYP-D3) gave significantly shorter Cu-Cu distances than those obtained using B3LYP, with the nondispersion-corrected calculations better matching the crystallographic data; other intramolecular metrics are better reproduced using B3LYP-D3. A discussion of the factors leading to this unusual observation is presented.

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Section: Resultsmentioning

confidence: 60%

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

et al. 2017

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“…The complex (CuR 4 tmsI) 2 (R 4 -tms ) pentamethylenethiuram monosulfide) displays a solidstate structure similar to the iodo derivative found in the methyl series. 13 Complexes CuEt 4 tmsX (X ) Cl, Br) 25 and CuPr 4 tmsBr (Pr ) n-propyl, i-propyl) 26 feature monomeric structures incorporating tricoordinate copper(I).…”

Section: Resultsmentioning

confidence: 99%

Crystal and Molecular Structures of a Neutral Pentanuclear Copper(I)−Iodide Complex

et al. 1998

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“…The reduction of the Cu(III) center could take place through the reductive elimination of two of the thiolate functions to form a disulfide-bridged dinuclear Cu(I) intermediate such as B (Scheme , path 1), which would then undergo sulfur abstraction by the displaced phosphine. Tetraalkylthiuram disulfides R 2 NC(S)SSC(S)NR 2 have been reported to undergo a similar reaction when treated with Cu(I) halides in the presence of PPh 3 , which leads to the formation of complexes containing the corresponding monosulfide R 2 NC(S)SC(S)NR 2 . An alternative reduction process could involve the direct attack of a phosphine to one of the sulfur atoms of the dithiolato ligand (Scheme , path 2).…”

Section: Resultsmentioning

confidence: 99%

“…The . 21 An alternative reduction process could involve the direct attack of a phosphine to one of the sulfur atoms of the dithiolato ligand (Scheme 4, path 2). In either case, the condensed ligand III in 3b and 6a-c presumably results from the nucleophillic attack of a dithiolate to the thioketene compound (2,7-di-tert-butylfluoren-9-ylidene)methanethione (V, Chart 1), which may exist as a coordinated ligand (intermediate C) or as short-lived free species after the sulfur abstraction.…”

Section: Synthesis Ofmentioning

confidence: 99%

Dinuclear Copper(I) and Copper(I)/Silver(I) Complexes with Condensed Dithiolato Ligands¹

Vicente¹,

González‐Herrero²,

Garcı́a-Sánchez³

et al. 2008

Inorg. Chem.

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The Cu(III) complex Pr 4N[Cu{S 2C=( t-Bu-fy)} 2] ( 1) ( t-Bu-fy = 2,7-di- tert-butylfluoren-9-ylidene) reacts with [Cu(PR 3) 4]ClO 4 in 1:1 molar ratio in MeCN to give the dinuclear complexes [Cu 2{[SC=( t-Bu-fy)] 2S}(PR 3) n ] [ n = 2, R = Ph ( 2a); n = 3, R = To ( 3b); To = p-tolyl]. The analogue of 2a with R = To ( 2b) can be obtained from the reaction of 3b with 1/8 equiv of S 8. Compound 2b establishes a thioketene-exchange equilibrium in solution leading to the formation of [Cu 4{S 2C=( t-Bu-fy)} 2(PTo 3) 4] ( 4b) and [Cu 2{[SC=( t-Bu-fy)] 3S}(PTo 3) 2] ( 5b). Solid mixtures of 4b and 5b in varying proportions can be obtained when the precipitation of 2b is attempted using MeCN. The reactions of 1 with AgClO 4 and PPh 3, PTo 3 or PCy 3 in 1:1:4 molar ratio in MeCN afford the heterodinuclear complexes [AgCu{[SC=( t-Bu-fy)] 2S}(PR 3) 3] [R = Ph ( 6a), To ( 6b), Cy ( 6c)]. Complex 6c dissociates PCy 3 in solution to give the bis(phosphine) derivative [AgCu{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 7c), which undergoes the exchange of [M(PCy 3)] (+) units in CD 2Cl 2 solution to give small amounts of [Cu 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 2c) and [Ag 2{[SC=( t-Bu-fy)] 2S}(PCy 3) 2] ( 8c). Complexes 6a and b participate in a series of successive equilibria in solution, involving the dissociation of phosphine ligands and the exchange of [M(PCy 3)] (+) units to give 2a or 3b and the corresponding disilver derivatives [Ag 2{[SC=( t-Bu-fy)] 2S}(PR 3) 2] [R = Ph ( 8a), To ( 8b)], followed by thioketene-exchange reactions to give [AgCu{[SC=( t-Bu-fy)] 3S}(PR 3) 2] [R = Ph ( 9a), To ( 9b)]. Complexes 9a and b can be directly prepared from the reactions of 1 with AgClO 4 and PPh 3 or PTo 3 in 1:1:3 molar ratio in THF. The crystal structures of 3b, 6b, 6c, 7c, and 9a have been solved by single-crystal X-ray diffraction studies and, in the cases of 7c and 9a, reveal the formation of short Ag...Cu metallophilic contacts of 2.8157(4) and 2.9606(6) A, respectively.

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Syntheses, properties, crystal and molecular structure of a novel neutral pentanuclear copper(I) iodide species. Copper(I) complexes with tetraethylthiuram monosulfide ‡

Cited by 14 publications

References 21 publications

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

Crystal and Molecular Structures of a Neutral Pentanuclear Copper(I)−Iodide Complex

Dinuclear Copper(I) and Copper(I)/Silver(I) Complexes with Condensed Dithiolato Ligands¹

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Syntheses, properties, crystal and molecular structure of a novel neutral pentanuclear copper(I) iodide species. Copper(I) complexes with tetraethylthiuram monosulfide ‡

Cited by 14 publications

References 21 publications

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

Synthesis, Structure, and Luminescence of Copper(I) Halide Complexes of Chiral Bis(phosphines)

Crystal and Molecular Structures of a Neutral Pentanuclear Copper(I)−Iodide Complex

Dinuclear Copper(I) and Copper(I)/Silver(I) Complexes with Condensed Dithiolato Ligands1

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Dinuclear Copper(I) and Copper(I)/Silver(I) Complexes with Condensed Dithiolato Ligands¹