Research

Jump to: Review

24 pages, 6622 KiB

Open AccessArticle

Binuclear Heteroleptic Ru(III) Dithiocarbamate Complexes: A Step towards Tunable Antiproliferative Agents

by Andrea E. Gallio, Leonardo Brustolin, Nicolò Pettenuzzo and Dolores Fregona

Inorganics 2022, 10(3), 37; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10030037 - 17 Mar 2022

Cited by 3 | Viewed by 2569

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Figure 1

13 pages, 2697 KiB

Open AccessArticle

Silver(I) and Gold(I) Monothiocarbonate Complexes: Synthesis, Structure, Luminescence

by Welni Duminy, Michael N. Pillay and Werner E. van Zyl

Inorganics 2022, 10(2), 19; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10020019 - 09 Feb 2022

Cited by 1 | Viewed by 2057

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Graphical abstract

13 pages, 6922 KiB

Open AccessArticle

Testing the Efficacy of the Synthesis of Iron Antimony Sulfide Powders from Single Source Precursors

by Fadiyah Makin, Dalal Alzahrani, Firoz Alam, Floriana Tuna and David J. Lewis

Inorganics 2021, 9(8), 61; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9080061 - 02 Aug 2021

Cited by 4 | Viewed by 2733

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, Fe_xS_y, and mixed iron antimony sulfide Sb_2(1−x)Fe_2xS₃ (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 Sb_2(1−x)Fe_2xS₃ (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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Figure 1

Review

Jump to: Research

14 pages, 2941 KiB

Open AccessReview

The Coordination Chemistry of Imidomethanedithiolate Di-anions: A Structural Comparison with Their Dithiocarbamate Analogs

by Peter J. Heard, Yee Seng Tan, Chien Ing Yeo and Edward R. T. Tiekink

Inorganics 2021, 9(9), 71; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090071 - 14 Sep 2021

Cited by 1 | Viewed by 2355

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Graphical abstract

48 pages, 11741 KiB

Open AccessReview

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

by Graeme Hogarth and Damian C. Onwudiwe

Inorganics 2021, 9(9), 70; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9090070 - 10 Sep 2021

Cited by 28 | Viewed by 6398

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Graphical abstract

41 pages, 7723 KiB

Open AccessReview

Dithiocarbamate Complexes of Platinum Group Metals: Structural Aspects and Applications

by Yee Seng Tan, Chien Ing Yeo, Edward R. T. Tiekink and Peter J. Heard

Inorganics 2021, 9(8), 60; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9080060 - 22 Jul 2021

Cited by 23 | Viewed by 4350

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Graphical abstract

25 pages, 1516 KiB

Open AccessReview

Insights into the Antimicrobial Potential of Dithiocarbamate Anions and Metal-Based Species

by Chien Ing Yeo, Edward R. T. Tiekink and Jactty Chew

Inorganics 2021, 9(6), 48; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9060048 - 14 Jun 2021

Cited by 16 | Viewed by 4107

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures

Graphical abstract

25 pages, 5114 KiB

Open AccessReview

A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

by See Mun Lee and Edward R. T. Tiekink

Inorganics 2021, 9(1), 7; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010007 - 15 Jan 2021

Cited by 14 | Viewed by 3051

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

(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)

► Show Figures