Special Issue "Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: 30 June 2022 | Viewed by 8126

Special Issue Editor

Dr. Graeme Hogarth
E-Mail Website
Guest Editor
Department of Chemistry, King’s College London, 7 Trinity Street, London SE1 1DB, UK
Interests: binuclear complexes; cluster chemistry; homogeneous catalysis; metals in medicine; hydrogenase biomimetics; dithiocarbamates; single source precursors

Special Issue Information

Dear Colleagues,

Dithiocarbamates (R2NCS2) have been known for approximately 150 years and have applications in areas as diverse as medicine, agriculture, biological imaging, and materials science. They are extremely versatile ligands, forming stable complexes with all of the transition metals, along with the lanthanides, the actinides, and a majority of the p-block elements, while their ability to adopt resonance hybrids allows for the stabilization of metals in both high and low oxidation states. Over the past decade, the development of dithiocarbamate chemistry has continued unabated with applications in areas including single-source precursors to nanoscale metal sulfides, co-ligands in a range of novel inorganic drugs, capping agents for nano-engineered surfaces and other nanomaterials including quantum dots, and the rational construction of well-defined complex molecular structures. The ever-increasing necessity to develop so-called Green Chemistry also plays into the hands of dithiocarbamate ligands as they are rapidly produced in high yields at room temperature from cheap and readily available primary and secondary amines, reactions often carried out in water and with 100% atom efficiency. In this Special Issue of Inorganics, we seek to bring together a diverse range of research on dithiocarbamate chemistry to highlight their continuing relevance, applicability, and versatility. All aspects of dithiocarbamate chemistry will be considered together with those of related ligands, such as xanthates and other dithiolates.

Dithiocarbamates are simple but highly versatile ligands that have played a major role in the development of transition metal chemistry and materials science over the past 150 years. They remain of great interest, a SciFinder© search showing that, over the past 20 years, approximately 15,000 publications have focused on this area. In this Special Issue of Inorganics, we hope to showcase recent advances in the wide-ranging coordination chemistry, materials science, and other applications of dithiocarbamates. In putting together a list of potential contributors, I have selected you on the basis of your previous outstanding contributions to this area and it gives me great pleasure to invite you to contribute to this Special Issue.

If you are interested in participating in this Special Issue, we would appreciate it if you would be so kind as to inform us of your intentions and send us a tentative title for your prospective contribution if you have one at this time.

Dr. Graeme Hogarth
Guest Editor

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • dithiocarbamate
  • versatile ligands
  • single-source precursors
  • materials chemistry
  • variable oxidation states

Published Papers (8 papers)

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Research

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Article
Binuclear Heteroleptic Ru(III) Dithiocarbamate Complexes: A Step towards Tunable Antiproliferative Agents
Inorganics 2022, 10(3), 37; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10030037 - 17 Mar 2022
Viewed by 646
Abstract
Binuclear dithiocarbamate complexes of Ru(III) are promising candidates in the search for outstanding metal-based anticancer agents. While different dithiocarbamates have shown ligand-dependent cytotoxicity in homoleptic binuclear Ru(III) complexes, the properties of heteroleptic analogues with different dithiocarbamate (DTC) ligands have yet to be explored. [...] Read more.
Binuclear dithiocarbamate complexes of Ru(III) are promising candidates in the search for outstanding metal-based anticancer agents. While different dithiocarbamates have shown ligand-dependent cytotoxicity in homoleptic binuclear Ru(III) complexes, the properties of heteroleptic analogues with different dithiocarbamate (DTC) ligands have yet to be explored. We herein propose the introduction of heteroleptic ligands as tunable features for the development of improved ruthenium-based antiproliferative agents and report a synthetic strategy for their synthesis as well as the evaluation of the cytotoxic activity of a selection of binuclear heteroleptic Ru(III) compounds towards MDA-MB-231 and PC3 cells. Full article
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Article
Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence
Inorganics 2022, 10(2), 19; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10020019 - 09 Feb 2022
Viewed by 531
Abstract
The monothiocarbonate ligand, [S(O)COR], is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag4(SC(O)OiPr)2(2,2′-bpy)4}(PF6 [...] Read more.
The monothiocarbonate ligand, [S(O)COR], is unusual and rare regarding its use in the formation of coordination compounds. Here, we report the synthesis and structures of the silver(I) and gold(I) monothiocarbonate complexes, [{Ag4(SC(O)OiPr)2(2,2′-bpy)4}(PF6)2]n (1) and [Au2{S(O)COiPr}2(dppe)]n (2), respectively. Both complexes are coordination polymers, with 1 being cationic and 2 neutral. The uniqueness of the ligand is that it is monoanionic and contains both a ‘hard’ O-donor ligand and a ‘soft’ S-donor ligand in a O-C-S manifold with, in principle, electron delocalization across the three atoms. However, for both complexes 1 and 2, it was found that the binding occurred exclusively through the S-donor atom, while the C=O portion remained dangling and was not involved in bonding. This bonding mode departs significantly from the symmetrical S-C-S type ligand such as dithiocarbamates. The structures were analysed and confirmed by NMR and X-ray crystallography. Full article
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Article
Testing the Efficacy of the Synthesis of Iron Antimony Sulfide Powders from Single Source Precursors
Inorganics 2021, 9(8), 61; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9080061 - 02 Aug 2021
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Abstract
The antimony-iron sulfide system in general does not produce alloys below 540 °C from traditional solid-state methods. However, single source precursors have been known to produce unexpected products that arise from kinetically trapped polymorphs. In this paper, we test the efficacy of this [...] Read more.
The antimony-iron sulfide system in general does not produce alloys below 540 °C from traditional solid-state methods. However, single source precursors have been known to produce unexpected products that arise from kinetically trapped polymorphs. In this paper, we test the efficacy of this approach toward the Fe-Sb-S system. Antimony and iron diethyldithiocarbamate complexes of the form Sb[S2CN(Et2)]3 (1) and Fe[S2CN(Et2)]3 (2) were synthesised, characterised, and used as single-source precursors for the preparation of Sb2S3, FexSy, and mixed iron antimony sulfide Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1) powders using the solvent-less thermolysis method at different temperatures ranging from 300 to 475 °C. The effect of different mole fractions of the iron precursor was evaluated on morphology, shape, and optical and magnetic properties of Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1). The obtained powders were characterized by X-ray diffraction (XRD), Raman spectroscopy scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, magnetometer measurement, and UV/vis/NIR spectroscopy. The results demonstrated that the crystalline structure, morphology, and elemental composition of the samples changed with the mole fraction of the precursor. There was significant phase separation between Sb and Fe sulfides noted from EDX spectroscopic mapping, yet an optoelectronic study monitoring the direct band gap energy of antimony sulfide shows that the band gap energy increases as a function of Fe content, which suggests limited alloying is possible from the single source route. Full article
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Review

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Review
The Coordination Chemistry of Imidomethanedithiolate Di-anions: A Structural Comparison with Their Dithiocarbamate Analogs
Inorganics 2021, 9(9), 71; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090071 - 14 Sep 2021
Viewed by 813
Abstract
A review of the coordination chemistry along with the structural features of heavy element complexes of dithiocarbimate di-anions in the form of [(R)C=NCS2]2− for R = CN, alkyl, and aryl are described. This class of compound is far less studied [...] Read more.
A review of the coordination chemistry along with the structural features of heavy element complexes of dithiocarbimate di-anions in the form of [(R)C=NCS2]2− for R = CN, alkyl, and aryl are described. This class of compound is far less studied compared with the well-explored dithiocarbamate mono-anions formulated as [R(R’)NCS2] for R/R’ = H, alkyl, and aryl. The coordination chemistry of dithiocarbimate di-anions is dominated by a S,S-chelating mode; rare examples of alternative modes of coordination are evident. When comparisons are available, the structural motifs adopted by metal dithiocarbimate complexes match those found for their dithiocarbamate analogs, with only small, non-systematic variations in the M–S bond lengths. Full article
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Review
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 - 10 Sep 2021
Cited by 2 | Viewed by 1187
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 [...] Read more.
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. Full article
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Review
Dithiocarbamate Complexes of Platinum Group Metals: Structural Aspects and Applications
Inorganics 2021, 9(8), 60; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9080060 - 22 Jul 2021
Cited by 6 | Viewed by 1045
Abstract
The incorporation of dithiocarbamate ligands in the preparation of metal complexes is largely prompted by the versatility of this molecule. Fascinating coordination chemistry can be obtained from the study of such metal complexes ranging from their preparation, the solid-state properties, solution behavior as [...] Read more.
The incorporation of dithiocarbamate ligands in the preparation of metal complexes is largely prompted by the versatility of this molecule. Fascinating coordination chemistry can be obtained from the study of such metal complexes ranging from their preparation, the solid-state properties, solution behavior as well as their applications as bioactive materials and luminescent compounds, to name a few. In this overview, the dithiocarbamate complexes of platinum-group elements form the focus of the discussion. The structural aspects of these complexes will be discussed based upon the intriguing findings obtained from their solid- (crystallographic) and solution-state (NMR) studies. At the end of this review, the applications of platinum-group metal complexes will be discussed. Full article
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Review
Insights into the Antimicrobial Potential of Dithiocarbamate Anions and Metal-Based Species
Inorganics 2021, 9(6), 48; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9060048 - 14 Jun 2021
Cited by 6 | Viewed by 1133
Abstract
Bacterial infection remains a worldwide problem that requires urgent addressing. Overuse and poor disposal of antibacterial agents abet the emergence of bacterial resistance mechanisms. There is a clear need for new approaches for the development of antibacterial therapeutics. Herein, the antibacterial potential of [...] Read more.
Bacterial infection remains a worldwide problem that requires urgent addressing. Overuse and poor disposal of antibacterial agents abet the emergence of bacterial resistance mechanisms. There is a clear need for new approaches for the development of antibacterial therapeutics. Herein, the antibacterial potential of molecules based on dithiocarbamate anions, of general formula R(R’)NCS2(−), and metal salts of transition metals and main group elements, is summarized. Preclinical studies show a broad range of antibacterial potential, and these investigations are supported by appraisals of possible biological targets and mechanisms of action to guide chemical syntheses. This bibliographic review of the literature points to the exciting potential of dithiocarbamate-based therapeutics in the crucial battle against bacteria. Additionally, included in this overview, for the sake of completeness, is mention of the far fewer studies on the antifungal potential of dithiocarbamates and even less work conducted on antiparasitic behavior. Full article
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Review
A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain
Inorganics 2021, 9(1), 7; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010007 - 15 Jan 2021
Cited by 8 | Viewed by 1165
Abstract
An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2 residues. In all, there are 40 different ligands of this type that [...] Read more.
An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2 residues. In all, there are 40 different ligands of this type that have been characterised crystallographically in their heavy-element compounds with up to six NCS2 residues; all are bridging. In most cases, the resulting aggregates are zero-dimensional, often di-nuclear, but aggregates of up to 36 metal (gold) atoms are noted. There are smaller numbers of one-, two-, and three-dimensional architectures sustained by poly-functional dithiocarbamate ligands in their respective crystals. The survey highlights the opportunities afforded by this generally under-studied class of ligand. Full article
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