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
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
Citations
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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)
TL;DR: A new mononuclear Cu(Ⅱ) dithiocarbamate complex was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction as discussed by the authors.
Journal ArticleDOI
Supramolecular assembly and structural transformation of d10-metal complexes containing (aza-15-crown-5)dithiocarbamate.
TL;DR: In this paper , the reaction of potassium (aza-15-crown-5)dithiocarbamate (KO4NCS2) and (Me2S)AuCl gave the dinuclear complex [Au(O4 NCS2)]2.
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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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In vitro biological studies of heteroleptic Ag(I) and Cu(I) unsymmetrical N,N′-diarylformamidine dithiocarbamate phosphine complexes; the effect of the metal center
TL;DR: A series of five dithiocarbamate and their respective Ag(I) and Cu(I)-triphenylphosphine complexes of the general formula [Ag/Cu(PPh3)2L] were synthesized and characterized as discussed by the authors.
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Journal ArticleDOI
Synthesis, crystal structure and photoconductivity of the first [60]fullerene complex with metal diethyldithiocarbamate: {CuII(dedtc) 2}2·C60
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TL;DR: The first molecular complex of fullerene C60 with metal dithiocarbamate, namely, {CuII(dedtc)2}2, was obtained as single crystals and the photoconductivity spectrum of 1 has a maximum at 470 nm showing that both intermolecular charge transfer between neighboring C60 molecules and photoexcitation of CuII (dedTC)2 can contribute to photogeneration of free charge carriers.
Journal ArticleDOI
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Journal ArticleDOI
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