Lead(II) in a sulfur-rich environment: Synthesis and molecular structure of the first dinuclear bis(mercaptoimidazolyl)methane complex

Pinder, Tiffany A.; VanDerveer, Donald G.; Rabinovich, Daniel

doi:10.1016/j.inoche.2007.08.015

Cited by 12 publications

(6 citation statements)

References 18 publications

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“…For all the copper complexes 1-8, the 1 H NMR resonances for the methyl and olefinic protons of the copper-bound dmise or dmit ligands are shifted downfield relative to unbound dmise or dmit, consistent with reports by Lobana, et al, 20,21,55 Rabinovich, et al, 68 and Kimani, et al 19 In the 13 C{ 1 H} NMR spectra, upfield shifts of the C-2 resonance of the dmise and dmit (both d ~6) are also observed upon copper complexation. Similar upfield shifts for the C Se or C S carbon atoms were observed for the Cu + complexes [Tpm R Cu(L)] + and Tp*Cu(L) (L = dmit or dmise) 19 The downfield shift of the olefinic proton resonances in the 1 H NMR spectra, as well as similar downfield shifts of the C-4 and C-5 resonances in the 13 C{ 1 H} NMR spectra, are indicative of metal complexation and concomitant weakening of the C S/Se bond.…”

Section: Crystallographic Studies Of Cu(i) Halides With Heterocyclic ...supporting

confidence: 87%

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

2011

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Coordination of Cu(I) halides with N,N'-dimethylimidazole selone (dmise) and thione (dmit) ligands was examined by treating CuX (X = Cl, Br, I) with one or two equivalents of dmise or dmit. The reaction of CuI and CuBr with one molar equivalent of dmise results in unusual selenium-bridged tetrameric Cu(4)(μ-dmise)(4)(μ-X)(2)X(2) copper complexes with average Cu-Se bond lengths of 2.42 Å and a Cu(2)(μ-X)(2) core (X = I (1) or Br (6)) that's in a rhomboidal structure. The reaction of CuX (X = Cl, Br, and I) with two equivalents of dmit or dmise results in trigonal planar Cu(I) complexes of two different conformations with the formula Cu(dmit)(2)X (3a, 3b, 4, and 7) or Cu(dmise)(2)X (2, 5, and 8) with average Cu-S and Cu-Se bond lengths of 2.23 Å and 2.34 Å, respectively. The coordination geometry around the copper center in complexes 1 to 8 is determined by the type of halide and chalcogenone ligand used, intramolecular π-π interactions, and short contact interactions between X-H (X = I, Br, Cl, Se or S). The theoretical DFT calculations are in good agreement with experimental X-ray structural data and indicate that dmise ligands are required for formation of the tetrameric complexes 1 and 6. Electrochemical studies show that the trigonal copper selone complexes have more negative potentials relative to analogous copper thione complexes by an average of 108 mV.

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Section: Crystallographic Studies Of Cu(i) Halides With Heterocyclic ...supporting

confidence: 87%

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

2011

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“…13 There is also increased interest in copper chalcogenolates as single-source precursors in the synthesis of semiconductor materials via metal organic chemical vapor deposition. 14 Although coordination complexes of the Bmm Me ligand with rhenium(I), 3 iron(II), 15 cobalt(II), 11 rhodium(I), 1,16 iridium(I), 17 nickel(II), 11 silver(I), 18,19 gold(I/III), 19 zinc(II), 20 tin(II), 21 lead(II) 22,23 and antimony(III) 8 have been isolated, it is rather surprising that only one report of copper(I) derivatives has been published, 19 particularly given the reported affinity of copper for sulfur-and selenium-containing ligands. 24 In this work, we report the synthesis and crystal structures of a series of dinuclear, three-and four-coordinate copper(I) complexes with the aim of understanding the effect of the methylene linkers and chalcogenone donor groups on the redox potentials of the Cu(I)/Cu(II) couple.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear copper(i) complexes with N-heterocyclic thione and selone ligands: synthesis, characterization, and electrochemical studies

et al. 2015

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The synthesis, characterization, and structures of a series of homoleptic and heteroleptic copper(I) complexes supported by N-heterocyclic chalcogenone ligands is reported herein. The quasi-reversible Cu(II/I) reduction potentials of these copper complexes with monodentate (dmit or dmise) and/or bidentate (Bmm(Me), Bsem(Me), Bme(Me), Bsee(Me)) chalcogenone ligands are highly dependent upon the nature and number of the donor groups and can be tuned over a 470 mV range (-369 to 102 mV). Copper-selone complexes have more negative Cu(II/I) reduction potentials relative to their thione analogs by an average of 137 mV, and increasing the number of methylene units linking the heterocyclic rings in the bidentate ligands results in more negative reduction potentials for their copper complexes. This ability to tune the copper reduction potentials over a wide range has potential applications in synthetic and industrial catalysis as well as the understanding of important biological processes such as electron transfer in blue copper proteins and respiration.

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“…Mixed anion complexes are attractive due to their potential applications and their new structures. In recent years, many researchers have undertaken considerable work on the synthesis of new silver(I) coordination polymers with flexible dithioether ligands. − However, the coordination chemistry of the flexible organochalcogenone ligands 1,n-bis(3-methylimidazole-2-thione) alkane has not been studied in detail in spite of their potential applications in the biomedical science as well as their interesting structural coordination chemistry. − The sulfur atom in dithione ligands has two lone pair electrons that can take part in coordination to metal ions. The S donors of dithione ligands coordinate to silver ion with monodentate, μ 2 -S and μ 3 -S bridging or chelating, combining bridging coordination modes and expanding the coordination sphere of the metal centers into extended solid-state networks. − On the other hand, the silver(I) ion is a soft Lewis acid and hence has a good ability to coordinate to a sulfur atom of a dithione that is a soft Lewis base .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structural Characterization, Photophysical Properties, and Antibacterial Assessment of Silver(I)-Thione Coordination Polymers Based on a Competition between Nitrate Anion and Coanions CF₃SO₃^–, ClO₄^–, BF₄^–, PF₆^–, and SbF₆^–

Soleymani-Babadi

Beheshti

Bahrani‐Pour

et al. 2019

Crystal Growth & Design

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Six new coordination polymers, namely, [Ag 2 L-(NO 3 ) 2 ] n (1), {[Ag 6 L 4 (CF 3 SO 3 ) 4 ][CF 3 SO 3 ] 2 } n (2), {[Ag 2 L-(NO 3 )][ClO 4 ]} n (3), {[Ag 2 L(NO 3 )][BF 4 ]} n (4), {[Ag 2 L(NO 3 )]-[PF 6 ]} n (5), and {[Ag 2 L(NO 3 )][SbF 6 ]} n (6), have been successfully synthesized by the reaction of AgNO 3 and selected coanions CF 3 SO 3 − , ClO 4 − , BF 4 − , PF 6 − , and SbF 6− with 1,3-bis(1methylthioimidazolyl) propane under the same experimental conditions in order to illustrate coordination ability of nitrate ion relative to the other considered coanions. To evaluate this competition, compound 1 as a reference structure was synthesized in the absence of coanions. In its two-dimensional structure, the thione ligand appears in a hexadentate mode, and the nitrate as a coligand is coordinated in a bidentate fashion. In a competition between the silver nitrate and triflate, despite the coordination ability expected for both anions, these anions did not appeared together in the structure of compound. The moderately coordinating anion CF 3 SO 3 − build up a cationic structure with only one kind of anion. In contrast to polymers 1 and 2, in the valuable networks 3−6, for the first time extraordinarily two kind of anions were involved in their structures. The difference between the coordination ability of the considered coanions is the most effective factor that impacts the coordination and linkage modes of the flexible ligand and nitrate anion and in turn directs the construction of coordination polymers. In general, X-ray diffraction analysis reveals that the most changes in the structure of compounds 3−6 relative to the structure of 1 were generated by the bulky, uncoordinated anions PF 6 − and SbF 6 − . The thermogravimetric analysis experimental data reveal that these compounds start to decompose in the temperature range of 140−328 °C. In their electronic spectra, a sharp band at 246 nm due to the π → π* transitions in the CS moiety of the ligand is slightly red-shifted upon coordination of the ligand to Ag I ions via sulfur atoms. All of the synthesized compounds display strong blue emissions in the solid state. The title complexes possess antibacterial activity against the selected strain of Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Grampositive (Staphylococcus aureus, Bacillus subtilis) bacteria.

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Lead(II) in a sulfur-rich environment: Synthesis and molecular structure of the first dinuclear bis(mercaptoimidazolyl)methane complex

Cited by 12 publications

References 18 publications

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

Dinuclear copper(i) complexes with N-heterocyclic thione and selone ligands: synthesis, characterization, and electrochemical studies

Synthesis, Structural Characterization, Photophysical Properties, and Antibacterial Assessment of Silver(I)-Thione Coordination Polymers Based on a Competition between Nitrate Anion and Coanions CF₃SO₃^–, ClO₄^–, BF₄^–, PF₆^–, and SbF₆^–

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Lead(II) in a sulfur-rich environment: Synthesis and molecular structure of the first dinuclear bis(mercaptoimidazolyl)methane complex

Cited by 12 publications

References 18 publications

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

Synthesis, characterization, and DFT studies of thione and selone Cu(i) complexes with variable coordination geometries

Dinuclear copper(i) complexes with N-heterocyclic thione and selone ligands: synthesis, characterization, and electrochemical studies

Synthesis, Structural Characterization, Photophysical Properties, and Antibacterial Assessment of Silver(I)-Thione Coordination Polymers Based on a Competition between Nitrate Anion and Coanions CF3SO3–, ClO4–, BF4–, PF6–, and SbF6–

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Synthesis, Structural Characterization, Photophysical Properties, and Antibacterial Assessment of Silver(I)-Thione Coordination Polymers Based on a Competition between Nitrate Anion and Coanions CF₃SO₃^–, ClO₄^–, BF₄^–, PF₆^–, and SbF₆^–