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)
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.
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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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Journal ArticleDOI
Structure and magnetic properties of bis(N,N-diisopropyldithiocarbamato)copper(II)
TL;DR: The complex bis(N,N-diisopropyldithiocarbamato) copper(II), C 14 H 28 CuN 2 S 4, crystallizes in the space group P1 of the triclinic system with Z=2.559 (3) A, b=11.692 (3), c=7.629 (2), α=96.35 (2) o, β=96 as mentioned in this paper, and γ=88.78
Journal ArticleDOI
Synthesis and characterization of copper(II) dithiocarbamate complexes involving pyrrole and ferrocenyl moieties and their utility for sensing anions and preparation of copper sulfide and copper–iron sulfide nanoparticles
Journal ArticleDOI
Bis(dimethyldithiocarbamato)(pyridine)zinc and -copper(II) and Their Benzene Solvates: EPR and Solid-State Natural Abundance (13C, 15N) CP/MAS NMR
TL;DR: In this paper, the electron paramagnetic resonance method and solid-state 13C and 15N CP/MAS NMR spectroscopy were used to perform a comparative study of the compounds obtained.
Journal ArticleDOI
An atom efficient, single-source precursor route to plasmonic CuS nanocrystals
Patrick Bergstrom Mann,Iain J. McGregor,Struan Bourke,Mary Burkitt-Gray,Simon M. Fairclough,Michelle T. Ma,Graeme Hogarth,Maya Thanou,Nicholas J. Long,Mark Green +9 more
TL;DR: In this paper, the authors presented the synthesis of copper sulfide nanocrystals via the decomposition of a copper dithiocarbamate complex in water, which exhibited a hollow nanosphere morphology.
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CuII and AuIII Complexes with Glycoconjugated Dithiocarbamato Ligands for Potential Applications in Targeted Chemotherapy.
Nicolò Pettenuzzo,Leonardo Brustolin,Elisa Coltri,Alberto Gambalunga,Federica Chiara,Andrea Trevisan,Barbara Biondi,Chiara Nardon,Dolores Fregona +8 more
TL;DR: This work linked the dithiocarbamato moiety to the C1 position of three different monosaccharides: d‐glucose, d‐galactose, and d‐mannose to improve the selective accumulation of an anticancer metal payload in malignant cells and showed high cytotoxic activity toward the HCT116 colorectal human carcinoma cell line.
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