Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond
Graeme Hogarth,Damian C. Onwudiwe +1 more
- Vol. 9, Iss: 9, pp 70
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TLDR
Copper dithiocarbamates 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 as mentioned in this paper.Abstract:
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 A. 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.read more
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The Next Generation of Platinum Drugs: Targeted Pt(II) Agents, Nanoparticle Delivery, and Pt(IV) Prodrugs
TL;DR: There has been a surge of activity, based on a great deal of mechanistic information, aimed at developing nonclassical platinum complexes that operate via mechanisms of action distinct from those of the approved drugs.
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Synthesis of ternary copper antimony sulfide via solventless thermolysis or aerosol assisted chemical vapour deposition using metal dithiocarbamates
TL;DR: In this paper , two facile, low-temperature and inexpensive techniques (solventless thermolysis and aerosol-assisted chemical vapor deposition (AACVD)) for the preparation of binary digenite (Cu1.8S), chalcocite (cu2S) and stibnite (Sb2S3) and several phases of ternary copper-antimony-sulfide (Cu2xSb 2(1-x)Sy, where 0 ≤ x ≤ 1).
Synthesis and Crystal Structure of a New Cu(II) Dithiocarbamate Complex CuI(prdtc)(phen)
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Supramolecular assembly and structural transformation of d10-metal complexes containing (aza-15-crown-5)dithiocarbamate.
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Synthesis, crystal structure, DFT and Hirshfeld surface analysis of Ni(II) complexes: precursor for nickel sulfide nanoparticles
TL;DR: In this paper , the crystal structures of complexes 1, 3 and 4 were determined by single crystal X-ray diffraction and showed that the dithiocarbamate ligands are coordinated to the nickel atom in the bidentate manner and the central atom is four coordinated.
References
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Journal ArticleDOI
Cu(S2CNEt2)Cl-Catalyzed Reverse Atom-Transfer Radical Polymerization of Vinyl Monomers
Peng Li,Kun‐Yuan Qiu +1 more
TL;DR: A new copper catalyst containing chlorine and a photo-labile diethylthiocarbamoylthiyl group was successfully employed in the reverse ATRP of methyl methacrylate (MMA) as discussed by the authors.
Journal Article
Reactivity of copper(I) tetrahydroborates toward CS2 and SCNPh. structures of (PPh3)2Cu(μ-S2CSCH2SCS2)Cu(PPh3)2, (PPh3)2Cu(S2COEt), and (PPh3)2Cu(S2CNHPh).CHCl3
Journal ArticleDOI
An ionic liquid route to prepare copper sulphide nanocrystals aiming at photocatalytic applications
TL;DR: In this article, the use of ionic liquids as a reaction medium to produce copper sulphide nanocrystals whose crystalline phase depends on the synthesis conditions was investigated and the results indicated that the ionic liquid route described here has an impact on the copper sulphides produced and thereby on their performance as photocatalysts.
Journal ArticleDOI
Crystal structures of bis-(N-methyl-N-phenyldithiocarbamato)-nickel-(II) and -copper(II)
TL;DR: The crystal and molecular structures of the title compounds have been determined by single-crystal X-ray diffraction methods, using conventional Patterson and Fourier heavy-atom methods, followed by block-diagonal least-squares refinement to R 0·116 (Ni) and 0·125 (Cu) for 1106 and 1202 visually estimated independent observed reflections.
Journal ArticleDOI
Diethyldithiocarbamate (ditiocarb sodium) effect on arachidonic acid metabolism in human mononuclear cells. Glutathione peroxidase-like activity.
Mohammed Hosni,Nadia Meskini,Annie-France Prigent,Genevieve Anker,Catherine Joulain,Raphaelle El Habib,Michel Lagarde +6 more
TL;DR: Results indicate that DTC, through its "GPx-like" activity is able to modify the lipoxygenase cascade, and its ability to selectively reduce 15-HPETE known to stimulate immunosuppressive T-cells might help to explain its positive regulatory effect upon the immune system.
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