Copper(III) Dithiocarbamates. An Undergraduate Experimental Project with Unexpected Challenges

Victoriano, Luis I.

doi:10.1021/ed079p1252

Cited by 2 publications

(3 citation statements)

References 3 publications

(9 reference statements)

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“…A common structural motif is a coordination polymer (Figure 9a [91] (Figure 9c). Copper(III) dihalide complexes, [CuX2(S2CNR2)], are also known and can also be accessed from the addition of thionyl chloride to [Cu(S2CNR2)2] [93] or the oxidative addition of thiuram disulfides to CuX2 [13,78,94] (Figure 10). These complexes are diamagnetic, consistent with a square-planar d 8 configuration and have been confirmed in a crystal structure of [CuBr2(S2CNBu2)] [95].…”

Section: Copper(iii) Dithiocarbamate Complexesmentioning

confidence: 99%

“…Copper(I) dithiocarbamate complexes come in two main forms: As clusters in which the dithiocarbamates bind in a capping manner and as mononuclear species with phosphine or phosphite co-ligands. Tetranuclear clusters, [Cu(μ3-S2CNR2)]4, have been known Copper(III) dihalide complexes, [CuX 2 (S 2 CNR 2 )], are also known and can also be accessed from the addition of thionyl chloride to [Cu(S 2 CNR 2 ) 2 ] [93] or the oxidative addition of thiuram disulfides to CuX 2 [13,78,94] (Figure 10). These complexes are diamagnetic, consistent with a square-planar d 8 configuration and have been confirmed in a crystal structure of [CuBr 2 (S 2 CNBu 2 )] [95].…”

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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Section: Copper(iii) Dithiocarbamate Complexesmentioning

confidence: 99%

Section: Copper(i) Dithiocarbamate Complexesmentioning

confidence: 99%

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

Hogarth

Onwudiwe

2021

Inorganics

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“…The formation of above copper(III) complex and role of perchlorate ion (a bulky anion) in stabilizing the higher oxidation state of copper(III) complex are quite well known (Victoriano 2002;Golding et al 1972). The stoichiometry of the fungicide-copper(II) perchlorate reaction has also been established by potentiometric titrations of thiophanate methyl with copper(II) perchlorate in acetonitrile in the presence of BMIB ionic liquid.…”

Section: Resultsmentioning

confidence: 99%

Pulse polarographic determination of thiophanate methyl fungicide in relation to its soil adsorption study

et al. 2015

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Background: The environmental pollution caused by the extensive use of the pesticide thiophanate methyl is of great concern, because it is a category III acute toxicant and a suspected carcinogen. Method: A remarkably sensitive differential pulse polarographic method for the determination of thiophanate methyl has been developed. The method is based on the reaction of the fungicide with copper(II) perchlorate in the presence of butylmethylimidazolium bromide (ionic liquid) in acetonitrile. Results: The reaction product exhibits an analytical useful diffusion controlled peak at −180 mV (vs SCE), and the thiophanate methyl has been determined in the linearity range 1.25 × 10 −6 to 12.5 × 10 −6 mol L

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Copper(III) Dithiocarbamates. An Undergraduate Experimental Project with Unexpected Challenges

Cited by 2 publications

References 3 publications

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

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

Pulse polarographic determination of thiophanate methyl fungicide in relation to its soil adsorption study

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