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Review

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

1
Department of Chemistry, King’s College London, Britannia House, 7 Trinity Street, London SE1 1DB, UK
2
Department of Chemistry, Faculty of Natural and Agricultural Science, North-West University, Mafikeng Campus, Private Bag X2046, Mmabatho 2735, South Africa
*
Authors to whom correspondence should be addressed.
Academic Editor: Duncan H. Gregory
Received: 4 August 2021 / Revised: 20 August 2021 / Accepted: 23 August 2021 / Published: 10 September 2021
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. View Full-Text
Keywords: copper; dithiocarbamate; clusters; nanomaterials; disulfiram; anticancer agents copper; dithiocarbamate; clusters; nanomaterials; disulfiram; anticancer agents
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MDPI and ACS Style

Hogarth, G.; Onwudiwe, D.C. Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond. Inorganics 2021, 9, 70. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090070

AMA Style

Hogarth G, Onwudiwe DC. Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond. Inorganics. 2021; 9(9):70. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090070

Chicago/Turabian Style

Hogarth, Graeme, and Damian C. Onwudiwe 2021. "Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond" Inorganics 9, no. 9: 70. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090070

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