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
Reads0
Chats0
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
More filters
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.
Journal ArticleDOI
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.
Journal ArticleDOI
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
More filters
Journal ArticleDOI
Hydrido copper clusters supported by dithiocarbamates: oxidative hydride removal and neutron diffraction analysis of [Cu7(H){S2C(aza-15-crown-5)}6].
Ping-Kuei Liao,Ching-Shiang Fang,Alison J. Edwards,Samia Kahlal,Samia Kahlal,Jean-Yves Saillard,Jean-Yves Saillard,C. W. Liu +7 more
TL;DR: This is the first time that hydride encapsulated within a copper cluster can be released as H(2) via chemical means, and all complexes have been fully characterized by (1)H NMR, FT-IR, UV-vis, and elemental analysis.
Journal ArticleDOI
One-step synthesis of phosphorus-doped g-C3N4/Co3O4 quantum dots from vitamin B12 with enhanced visible-light photocatalytic activity for metronidazole degradation
TL;DR: In this paper, Co3O4 quantum dots decorated phosphorus-doped g-C3N4 nanosheets were synthesized through one-step thermal polymerization method using vitamin B12 (VB12) as precursor of cobalt and phosphorus mixed with melamine.
Journal ArticleDOI
Shape-controlled synthesis of semiconducting CuFeS2 nanocrystals
TL;DR: In this article, a facile solution-based method was used to synthesize chalcopyrite CuFeS 2 nanocrystals with either a spherical or pyramidal morphology with a narrow size distribution.
Journal ArticleDOI
Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes.
O. Danny Fox,James Cookson,Emma J. S. Wilkinson,Michael G. B. Drew,Elizabeth J. MacLean,and Simon J. Teat,Paul D. Beer +6 more
TL;DR: X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometry favor hexanuclear "molecular loop" structures.
Journal ArticleDOI
[Cu13 {S2 CNn Bu2 }6 (acetylide)4 ]+ : A Two-Electron Superatom.
Kiran Kumarvarma Chakrahari,Jian-Hong Liao,Samia Kahlal,Yu-Chiao Liu,Ming-Hsi Chiang,Jean-Yves Saillard,C. W. Liu +6 more
TL;DR: The first structurally characterized copper cluster with a Cu13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu13 (S2 CNn Bu2 )6 (C≡CR)4 ](PF6 ) (R=C(O)OMe, C6 H4 F) nanoclusters.
Related Papers (5)
Ternary copper-incorporated group 8 (Ru or Fe) carbonyl chalcogenide complexes and polymers: From syntheses to applications
Minghuey Shieh,Chia Chi Yu +1 more