On Ammonium‐bis(dithiocarbamato)‐copper(I)‐monohydrate and Mono(dithiocarbamato)‐copper(I)

Teske, Chr. L.

doi:10.1002/zaac.201300321

Cited by 5 publications

(9 citation statements)

References 22 publications

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“…The investigation of the intermediate (XRPD) obtained at T ≈ 170 °C revealed that appreciable amounts of the final product (Ag 2 S) is formed at relatively low temperature, yet before all of the starting phase is decomposed. The absence of AgSCN21–23 as an intermediately formed compound is remarkable, which is in contrast to the homologue copper compound CuS 2 CNH 2 , where the corresponding thiocyanate CuSCN was detected as an intermediate compound 18. The thermal decomposition of AgSCN was investigated earlier,24,25 however not in inert gas atmosphere.…”

Section: Discussionmentioning

confidence: 99%

On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂

Teske

Bensch

2015

Zeitschrift anorg allge chemie

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The title compound AgS2CNR2 was prepared from an aqueous alcoholic solution by reaction of dicyanoargentate [Ag(CN)2]– with excess ammoniumdithiocarbamate. It crystallizes in the tetragonal space group I$\bar{4}$2d (No. 122) with a = 7.9898(4) and c = 12.1072(7) Å, V = 772.89(7) Å3, Z = 8. The crystal structure comprises a 3D tetrahedral network of distorted AgS4 units connected via all vertices thus forming the β‐cristobalite structure type. The dithiocarbaramate ligands extend into the hollow space of the framework. Thermal decomposition starts above 125 °C and proceeds with a complex reaction to give finally Ag2S (acanthite).

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Section: Discussionmentioning

confidence: 99%

On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂

Teske

Bensch

2015

Zeitschrift anorg allge chemie

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“…They contain an icosahedral Cu12 core, two faces of which are capped, while the final copper atom is encapsulated as a linear [CuH2] − moiety (Figure 14b). [114]. Somewhat unexpectedly, however, the structure does not show the expected [Cu(S 2 CNH 2 ) 2 ] − anion, but rather is a coordination polymer in which each dithiocarbamate ligand spans two copper centres (Figure 15a).…”

Section: Copper(i) Dithiocarbamate Complexesmentioning

confidence: 91%

“…80-95 • C, a second coordination polymer [Cu(S 2 CNH 2 )] n results. While each copper remains bound to four dithiocarbamates, the CuS 4 tetrahedral are now linked in a 3D array reminiscent of a filled β-cristobalite structure [114].…”

Section: Copper(i) Dithiocarbamate Complexesmentioning

confidence: 99%

“…As detailed earlier (Figure 7), [Cu(S2CNR2)2] can be quasi-reversibly reduced to Cu(I) anions, [Cu(S2CNR2)2] − , but until recently, no examples of these anionic Cu(I) complexes had ever been isolated, with all attempts leading to loss of a dithiocarbamate ligand with concomitant formation of Cu(I) clusters [Cu(S2CNR2)]n. In 2013, Teske reported the preparation and crystal structure of [NH4][Cu(S2CNH2)2]•H2O, formed upon the addition of [NH4][S2CNH2] to CuSO4 in the presence of KCN [114]. Somewhat unexpectedly, however, the structure does not show the expected [Cu(S2CNH2)2] − anion, but rather is a coordination polymer in which each dithiocarbamate ligand spans two copper centres (Figure 15a).…”

Section: Copper(i) Dithiocarbamate Complexesmentioning

confidence: 99%

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Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Hogarth

Onwudiwe

2021

Inorganics

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Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.

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“…Medium strong and very weak hydrogen bonds (N–H ··· S, Table 3) induce additional cohesion. Recently the closely related orthorhombic, filled β‐cristobalite like structure of the homologue copper compound CuS 2 CNH 2 was reported,18 where the distortion of the tetrahedra is clearly more pronounced.…”

Section: Resultsmentioning

confidence: 99%

Analysis and Mitigation of Electrochemical Impedance Spectroscopy Artefacts in Four‐Electrode Cells: Experimental Aspects

et al. 2015

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The analysis and minimization of the electrochemical spectroscopy impedance artefacts measured in a four‐electrode cell were addressed by using bypass modification of reference and sensing electrodes and capacitor bridges. Additionally, the influence of the resistance of the reference and sensing electrodes on the measured spectra was studied. Two types of four‐electrode cells, non‐zero gap and zero gap, were used for electrochemical impedance spectroscopy measurements in potassium phosphate buffer solution. Different impedance values of the reference and sensing Pb/PbF2 electrodes were achieved by varying the concentration of fluoride salt in the solution used to fill the electrodes. The artefacts occurring during the measurements were successfully minimized by improving the conductance of the reference and sensing electrodes at high frequencies through a bypass. Contrary to that previously observed for a three‐electrode setup, the use of capacitor bridges amplified the measured artefacts.

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On Ammonium‐bis(dithiocarbamato)‐copper(I)‐monohydrate and Mono(dithiocarbamato)‐copper(I)

Cited by 5 publications

References 22 publications

On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂

On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Analysis and Mitigation of Electrochemical Impedance Spectroscopy Artefacts in Four‐Electrode Cells: Experimental Aspects

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On Ammonium‐bis(dithiocarbamato)‐copper(I)‐monohydrate and Mono(dithiocarbamato)‐copper(I)

Cited by 5 publications

References 22 publications

On Mono(dithiocarbamato)‐silver(I), AgS2CNH2

On Mono(dithiocarbamato)‐silver(I), AgS2CNH2

Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond

Analysis and Mitigation of Electrochemical Impedance Spectroscopy Artefacts in Four‐Electrode Cells: Experimental Aspects

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On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂

On Mono(dithiocarbamato)‐silver(I), AgS₂CNH₂