Addressing misconceptions in dithiocarbamate chemistry

Abstract

Dithiocarbamates are monoanionic chelating ligands, easily prepared from CS₂ and secondary or primary amines, that find widespread use in agriculture, medicine, materials science and coordination chemistry. This is (in part) due to their ability to stabilise metals in a wide range of oxidation states, a result of soft (dithiocarbamate) and hard (thioureide) resonance forms. However, in the many thousands of publications on dithiocarbamate chemistry, some common misconceptions have arisen, often being accepted as truth. In this perspective we address some of these in the hope that, moving forward, the wider community will better grasp the nuances of the chemistry of this important ligand type.

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1. Introduction

Dithiocarbamates, their complexes, and oxidised counterparts the thiuram disulfides (Fig. 1) find widespread uses in a diverse range of areas including: agriculture,^1,2 analytical chemistry,^3–7 coordination chemistry,^8–18 environmental remediation,^19–23 medicine,^24–29 enzyme inhibition,^30–36 medical imaging,^37–39 living polymerisation,^40–43 materials science^44–48 and as precursors to metal-sulfide nanomaterials.^49–52 They are a subset of the widely studied 1,1′-dithiolate ligands and close relatives of thiocarbamates and carbamates.^8,9 Despite being known for at least 150 years they remain an area of significant research activity. For example, with the recent identification of a new cell death mechanism termed cuprotosis,⁵³ the anti-cancer activity of [Cu(S₂CNEt₂)₂], which has been known for over 40 years,^54–59 has once again come under the spotlight.^60–64 Thus, tetraethyl thiuram disulfide (Et₄TDS), better known as Disulfiram (Antabuse), is a drug that finds widespread use in the treatment of alcoholism.⁶⁵ It is rapidly metabolised in the gut (it is normally given orally) or in blood⁶⁶ to give diethyldithiocarbamate, which in turn can bind to Cu(II) to afford [Cu(S₂CNEt₂)₂] in situ.

Fig. 1 Dithiocarbamates, their complexes and thiuram disulfides.

Dithiocarbamates are easily prepared, generally in high yields, upon reaction of CS₂ with secondary or primary amines generally in the presence of an added base.⁸ Water is often used as the solvent, although reactions also proceed in MeOH and some other organic solvents. Reactions can be carried out in air, making dithiocarbamates easily accessible in less sophisticated lab environments. Consequently, this has led to an extremely large volume of research output: a search for “dithiocarbamate” in SciFinder© giving almost 25 000 hits and for “dithiocarbamato” another ca. 1500. Many of these publications are of excellent quality, some being cited thousands of times. However others contain errors and misconceptions, some of which are repeated so frequently as to be erroneously accepted as truth.

As researchers who are active in the area^67–72 and have written significant reviews,^8,24,49 we have read and closely scrutinised a considerable number of papers on dithiocarbamate chemistry. In doing so we have seen some errors-misconceptions being regularly repeated. In this contribution we address these, with the hope that they may appear less frequently in the future. In general, our intention is not to highlight individual contributions where errors have been made or perpetuated, however at times this is unavoidable. We accept that the majority are made in good faith and hope to avoid demonising individuals.

2. Synthesis of dithiocarbamates

(i) Amines are deprotonated by base, and it is the amide that undergoes nucleophilic attack at CS₂ to afford the dithiocarbamate

Primary and secondary amines are extremely basic, having pK_bs of ca. 4. Consequently, they are not acidic and have pK_as of ca. 40. Thus, upon dissolution in water (or an organic solvent), even following the addition of a strong base such as NaOH, they are not deprotonated. They are, however, nucleophilic and like many N-based nucleophiles can react directly with the electrophilic carbon in CS₂.⁷³ This generates a zwitterion which cannot be isolated or spectroscopically identified, presumably since the equilibrium lies to the left-hand side. It can, however, be deprotonated by the added base, which if it is a hydroxide then simply affords water and the desired dithiocarbamate (Fig. 2).

Fig. 2 Reaction of secondary amine with CS₂ in the presence of MOH as a base.

Unfortunately, there are many examples in the literature that show the secondary (or primary) amine being deprotonated by the base and then suggesting that it is the generated amide [NR₂]⁻ or [NHR]⁻ that reacts with CS₂. As stated above, most bases used in the formation of dithiocarbamates are not basic enough to deprotonate the amine, and even if they were, the generated amides are very susceptible to hydrolysis and would immediately regenerate the amine. We note that alkali metal amides such as LiNMe₂ are highly pyrophoric and should be handled in a rigorously anhydrous environment (also see section 2-iii).

(ii) In the absence of an added base, CS₂ reacts with a primary or secondary amine to afford the dithiocarbamic acid

Many secondary and primary amines react directly with CS₂ and do not require added base. Thus, it is tempting to suggest that the reaction furnishes the free dithiocarbamic acid. This is, however, erroneous and rather this reaction generates the corresponding ammonium salt of the dithiocarbamate (Fig. 3).

Fig. 3 Reaction of secondary amine with CS₂ in the absence of a second base.

Thus, it can be viewed in the same way as that above (Fig. 2), with the zwitterion being deprotonated by the amine which acts as both nucleophile and base. Thus, the overall stoichiometry is not 1 : 1 but rather 2 : 1, amine to CS₂.^74–76 Indeed, three purported crystal structures of dithiocarbamic acids have been reported^77–79 (one later revised).⁸⁰ The crystal structure of an adduct of hexylamine (HexNH₂) and the dithiocarbamic acid, HexNHCS₂H ⁷⁸ is really the ammonium salt (Fig. 4a), but the proton has been incorrectly located on sulfur rather than hexylamine. Likewise, in the proposed amino acid derivative (Fig. 4b) the proton is actually located on the basic nitrogen.⁷⁹

Fig. 4 Actual and proposed forms of crystallographically characterised “dithiocarbamic acids”.

Sometimes, even when a second base has been added, the ammonium dithiocarbamate is (in part) generated in the reaction especially when the amine is a strong base, as the two compete to deprotonate the zwitterion. This is the case in the reaction of ⁱBu₂NH and CS₂ in water with added NaOH, a reaction we have carried out numerous times in our lab. Thus, the off-white ammonium salt has poor water solubility and can precipitate, often being observed as a “scum” in the reaction vessel. Simply stirring in a warm (ca. 50–60 °C) water bath for 20–30 min leads to complete dissolution and formation of a clear pale-yellow solution of NaS₂CNBuⁱ₂.

Nice illustrations of an amine acting as both a base and a nucleophile are in the reaction of diamines with CS₂. For example, reaction of piperazine with CS₂ affords as the major product a zwitterionic product (Fig. 5) together with a small amount (ca. 5–10%) of the (so-called) double salt, thus providing an elegant method of desymmetrising a cheap diamine which can then be used to build up novel multimetallic arrays.^81–86

Fig. 5 Reaction of piperazine with CS₂.

(iii) Reactions of diarylamines with CS₂ in the presence of MOH afford diaryldithiocarbamates

Anilines are nucleophilic enough to react directly with CS₂ and thus dithiocarbamates, [ArNHCS₂]⁻ are readily available.⁸⁷ In contrast, diphenylamine and other diarylamines are not nucleophilic enough and will not react directly with CS₂ in the presence of standard bases. Thus, to prepare [Ar₂NCS₂]⁻, the corresponding amides [NAr₂]⁻ need to be accessed; these are nucleophilic enough to react with CS₂. Reagents that are basic enough to deprotonate Ar₂NH include ⁿBuLi,^88,89 NaBH₄,⁹⁰ sodium amide^91,92 and KOBu^t.⁶⁷ All require water-free conditions otherwise the neutral amines will simply be regenerated. Thus, we have recently developed a preparation⁸⁸ that uses ⁿBuLi in thf to afford LiNAr₂ at low temperatures, which in turn react with CS₂ to form LiS₂CNAr₂ in (essentially) quantitative yields⁶⁷ (Fig. 6). Once formed these dithiocarbamate salts are very stable and can be stored indefinitely as solids in air. We have also had success with using KOBu^t in thf but found this not to be reproducible in regular lab grade solvents. As stated above, other authors have used NaBH₄ but in our hands this was not successful.

Fig. 6 Generation of diaryldithiocarbamate salts upon addition of CS₂ to LiNAr₂.

(iv) Amides such as phthalimide and succinimide react with CS₂ to generate dithiocarbamates

As discussed above, amines need to be relatively nucleophilic if a dithiocarbamate is to be made directly, and amides are not nucleophilic enough to react directly with CS₂. Despite this, several publications claim the synthesis of amide-derived dithiocarbamates and their complexes,^93–97 some of which we have failed to reproduce.^93,94 As highlighted for diarylamines, a second approach is to initially deprotonate to yield the more nucleophilic anion. In this way, we have tried reacting commercially available sodium phthalimide with CS₂ under a variety of conditions but in all instances, we found no evidence for the formation of the corresponding dithiocarbamate (Fig. 7).

Fig. 7 Unsuccessful reaction of phthalimide with CS₂.

In contrast, 2-pyrrolidone does react with CS₂ in the presence of bases such as KOH, to afford a dithiocarbamate which can be quenched with electrophiles to give the corresponding ester.^98–100 Formamide also reacts with CS₂ in the presence of base as confirmed by the crystal structure of KS₂CNH(CHO).¹⁰¹ There is a short paper on metal complexes of 2-pyrrolidone dithiocarbamate,¹⁰² which suggests this ligand type could be further developed, along with that of iso-indolinone, for which the dithiocarbamate has not been reported but is likely accessible.

There are several authenticated examples of amide-functionalised dithiocarbamate complexes, being accessible via dithiocarbimate complexes.¹⁰³ For example, deprotonation of the corresponding primary amine-derived nickel complexes, [Ni(S₂CNHR)₂], followed by quenching with electrophiles such as acetic anhydride and benzoyl chloride (Fig. 8).^104–107 These amide-dithiocarbamate complexes are very stable and show interesting physical properties, something we have recently been reinvestigating in our own research.¹⁰⁷

Fig. 8 Synthesis and molecular structure (R = ⁱBu) of amide-functionalised nickel bis(dithiocarbamate) complex.

3. Stability of dithiocarbamates and thiuram disulfides

(i) Dithiocarbamic acids are stable and isolable entities

A major misconception in dithiocarbamate chemistry, being especially prevalent in the biological domain, is that dithiocarbamic acids are stable entities. Thus, as has been well studied, disulfiram is rapidly reduced in vivo to give two equivalents of diethyldithiocarbamate, which is often erroneously written as the free acid.¹⁰⁸ Chemists are also not immune to this mistake and often (as noted above) the direct reaction of an amine with CS₂ is purported to give the dithiocarbamic acid rather than the ammonium salt of the dithiocarbamate.^{77–79,109–112} Dithiocarbamates are basic, especially those with two alkyl substituents, and at pH 7 or below (indeed even above this in some cases) they are protonated to give the dithiocarbamic acids. However, these are unstable and, in most cases, decompose rapidly to give CS₂ and the corresponding ammonium salt (Fig. 9). Many publications have addressed the decomposition process, and mechanistic aspects have been elucidated.^113–124 Here is not the place to go into detail but the main decomposition route involves a hydrogen-bonded intermediate, rather than zwitterion formation resulting from proton transfer from sulfur to nitrogen. Decomposition is accelerated upon lowering the pH and this is why dithiocarbamates are generated under basic conditions. Recently, the generation and decomposition of dithiocarbamic acids has been repurposed as a route for the release of CS₂.¹²⁵ These studies show that their lifetimes are highly dependent upon the nature of the substituents, those with two aryl groups being stable for up to 24 h at pH 7.4.¹²⁵ Dithiocarbamic acids of primary amines are especially unstable¹¹⁹ but still appear in the literature.¹²⁶ Dithiocarbamates of primary amines are widely used as precursors for the generation of organic isothiocyanates^127,128 and other sulfur-containing organics.^129,130

Fig. 9 In situ generation and decomposition of dithiocarbamic acids.

(ii) Dithiocarbamate halides are accessible

A relatively uncommon misconception, but one that is increasingly appearing in the literature, is the idea that halides of dithiocarbamates, especially the iodide, are accessible.¹³¹ It is well known that iodine acts as an oxidising agent, converting dithiocarbamates into thiuram disulfides, rather than forming the corresponding iodide (Fig. 10). With primary amine dithiocarbamates this (likely) generates the unstable thiuram disulfide (see below), and not the iodide.^132,133

Fig. 10 I₂ oxidation of dithiocarbamate to thiuram disulfide.

It is worth adding that, while not a misconception, the redox chemistry of the dithiocarbamate ligand is often overlooked, which can lead to an over-simplification of discussion of redox events when coordinated to metal centres. Examples are reactions of [M(S₂CNR₂)₂] (M = Zn, Cd) with I₂.^134,135 Thus, reduction of iodine is rapid at the non-redox active Zn(II) centre as it is the dithiocarbamate that is oxidised, on metal, to form the corresponding thiuram disulfide complexes (Fig. 11).

Fig. 11 I₂ addition to [Zn(S₂CNR₂)₂] and formation of a thiuram disulfide complex.

(iii) Thiuram disulfides of primary amines are stable

Thiuram disulfides generated from secondary amines are generally very stable and can be easily isolated, purified and stored. Indeed, they are often easier to store than the corresponding dithiocarbamates and can then be reduced in situ to provide a source of dithiocarbamate. In contrast, oxidation of primary amine dithiocarbamates affords thiuram disulfides with poor stability, decomposing to afford isothiocyanates and/or thioureas, depending upon the reaction conditions used^{127,136–140} (Fig. 12).

Fig. 12 Formation and decomposition of primary amine thiuram disulfides.

4. Accessibility and air-stability of [M(S₂CNR₂)₂]

One of the beauties of doing transition metal dithiocarbamate chemistry is their ease of synthesis, isolation, and purification, much of which can be carried out in air. Thus, complexes normally have moderate to good solubility in polar organic solvents, and many can be crystallised in air, either by slow evaporation or the (careful) addition of an anti-solvent such as hexane or petroleum ether. In this way, the crystal structures of thousands of dithiocarbamate complexes have found their way into the Cambridge Crystallographic Data Centre (CCDC).¹⁴¹ However, not all dithiocarbamate complexes are air stable. For example, while bis(dithiocarbamate) complexes, [M(S₂CNR₂)₂] (M = Ni, Cu, Zn) are air and moisture stable, in contrast those of the other first row transition elements can only be prepared (if at all) under rigorously oxygen-free conditions.^142–144 Thus, generally, if they can be prepared, [M(S₂CNR₂)₂] complexes are readily oxidised in air, with M(III) complexes being favoured. Below we discuss each metal type individually as their chemistry differs. We also describe some related chemistry (where appropriate) to provide context.

(i) M = Ti, V, Cr

The chemistry of titanium is dominated by the +4 and +3 oxidation states, and dithiocarbamates are no exception. A Ti(II) complex has briefly been mentioned in the literature,¹⁴⁵ reaction of [Ti(NEt₂)₃] and CS₂ being reported to give a mixture of [Ti(S₂CNEt₂)₂] and [Ti(S₂CNEt₂)₄]. However, no characterising data or reaction details were given. The existence and stability of red Ti(IV) complexes [Ti(S₂CNR₂)₄] are without doubt, being prepared upon insertion of CS₂ into [Ti(NR₂)₄],¹⁴⁶ or upon addition of LiS₂CNR₂ to TiBr₄.¹⁴⁷ Both [Ti(S₂CNEt₂)₄]¹⁴⁸ and [Ti(S₂CNPrⁱ₂)₄]¹⁴⁷ have been crystallographically characterised. One report suggests that reaction of NaS₂CNR₂ with TiCl₃ in EtOH affords [Ti(S₂CNR₂)₃] as brown- or yellow-green solids,¹⁴⁹ but there are no later mentions of this type of complex in the literature. Thus, the stability of [Ti(S₂CNR₂)₃], their potential disproportionation to [Ti(S₂CNR₂)₂] and [Ti(S₂CNR₂)₄], and structure and stability of the former remain issues that require clarification. Interestingly, it has recently been established that dithiocarbamates can coordinate to Ti(0), thus, oxidation of [Ti(CO)₆]²⁻ by thiuram disulfides affords [Ti(CO)₄(S₂CNR₂)]⁻ which adopt an unexpected trigonal prismatic geometry.¹⁵⁰ There may yet be new things to discover in titanium dithiocarbamate chemistry.

The only V(II) dithiocarbamate complex reported is light brown [V(S₂CNEt₂)₂], formed under rigorously oxygen-free conditions upon addition of two equivalents of NaS₂CNEt₂ to VCl₂ in MeCN in a dry box.¹⁴³ Unfortunately, no characterising data was given, but it was reported to be soluble in warm 1,2-dichlorobenzene, so may be worthy of reinvestigation. In air, addition of [R₂NH₂][S₂CNR₂] to VBr₂·6H₂O affords [V(S₂CNR₂)₃].¹⁵¹ The diethyl derivative has been crystallographically characterised¹⁵² and magnetic measurements show a S = 1 ground state with two unpaired electrons.¹⁵³ Possibly, [V(S₂CNR₂)₂] are fleetingly formed but readily oxidised, and putative [V(S₂CNR₂)₂]⁺ reacts with further dithiocarbamate. The reduction chemistry of [V(S₂CNEt₂)₃] has been investigated and reveals a reversible one-electron process.¹⁵⁴ Eight-coordinate V(IV) complexes, [V(S₂CNR₂)₄], are accessible from the insertion of CS₂ into [V(NR₂)₄],¹⁵⁵ but upon heating they undergo intramolecular electron transfer resulting in elimination of thiuram disulfide and formation of [V(S₂CNR₂)₃]. Formal oxidation products of [V(S₂CNR)₂], namely vanadyl complexes [VO(S₂CNR₂)₂], are easily prepared¹⁵⁶ and have been extensively investigated as potential insulin mimetics¹⁵⁷ and molecular qubits.¹⁵⁸ Thus, akin to the titanium chemistry, even the simple dithiocarbamate chemistry of vanadium requires further investigation.

Chromium bis(dithiocarbamate) complexes are indisputably accessible, but extremely air sensitive, so unless rigorous experimental methods are utilised it is the analogous d³ Cr(III) complexes, [Cr(S₂CNR₂)₃] that are isolated.^159–161 The first synthesis of [Cr(S₂CNEt₂)₂] was reported by Fackler and Holah in 1966,¹⁶² being described as a pyrophoric yellow-green solid. It has subsequently been prepared from thermolysis of [Cr(CO)₆] and [Hg(S₂CNEt₂)₂].¹⁶³ In solution [Cr(S₂CNEt₂)₂] is extremely sensitive to air oxidation, converting rapidly to blue [Cr(S₂CNEt₂)₃]. Very few derivatives have been prepared and there are no crystal structure determinations, thus molecular structure(s) of [Cr(S₂CNR₂)₂] remain unknown, although most likely they are polymeric in the solid state, and tetrahedral in the gas phase or solution. Electrochemical studies of [Cr(S₂CNR₂)₃] show that they undergo a one-electron reduction, with the generated [Cr(S₂CNR₂)₃]⁻ rapidly losing a dithiocarbamate to give [Cr(S₂CNR₂)₂]¹⁶⁴ (Fig. 13). However, all attempts to isolate or characterise [Cr(S₂CNR₂)₂] generated in this way have led only to rapid back oxidation and regeneration of [Cr(S₂CNR₂)₃], again highlighting their extreme air-sensitivity.

Fig. 13 Formation of [Cr(S₂CNR₂)₂] via reduction of [Cr(S₂CNR₂)₃] and back oxidation.

Non-homoleptic Cr(II) dithiocarbamate complexes can be prepared. For example, room temperature addition of [CpCr(CO)₃]₂ and tetraethyl thiuram disulfide affords [CpCr(CO)₂(S₂CNEt₂)] in good yields.¹⁶⁵

(ii) M = Mo, W

We briefly consider the heavier group 6 homologues, [Mo(S₂CNR₂)₂] and [W(S₂CNR₂)₂]. The synthesis and X-ray crystal structure of [Mo(S₂CNEt₂)₂] has been claimed¹⁶⁶ but is erroneous: the structure presented is that of [Ni(S₂CNEt₂)₂] with a misassigned metal atom.¹⁶⁷ Complexes of the stoichiometry Mo : dithiocarbamate 1 : 2 are known. Thus, reactions of [Mo₂(μ-OAc)₄] with four equivalents of dithiocarbamate afford [Mo₂(μ-S₂CNR₂)₄] as green solids.¹⁶⁸ However, the latter are thermally unstable and upon heating undergo C–S bond scission to yield Mo(V) thiocarboxamide complexes, [Mo(μ-S)(S₂CNR₂)(SCNR₂)]₂ as shown crystallographically (R = ⁱPr).¹⁶⁹ Related W(II) complexes, [W(S₂CNR₂)₂], remain unreported, but both cis-[W(CO)₂(S₂CNR₂)₂] and [W(CO)₃(S₂CNR₂)₂] are known¹⁷⁰ as are the corresponding Mo(II) carbonyl complexes.¹⁷¹

(iii) [Mn(S₂CNR₂)₂]

Bright yellow [Mn(S₂CNR₂)₂] complexes can easily be prepared, but both the reaction and work-up must be carried out under rigorously inert conditions.^172,173 The molecular structure of only one example, namely [Mn(S₂CNEt₂)₂], has been reported (Fig. 14).¹⁷⁴ It is a coordination polymer containing octahedral Mn(II) centres resulting from the dithiocarbamates binding in a bridging manner.

Fig. 14 Part of the polymeric structure of [Mn(S₂CNEt₂)₂].¹⁷⁴

Many papers detail reactions of two equivalents of dithiocarbamates with Mn(II) salts that have been carried out in water and air, and invariably the generated products are dark (often violet-purple) paramagnetic solids formulated as [Mn(S₂CNR₂)₂]. Authors often cite elemental analysis data as proof of this formulation. Indeed, fits with calculated values are often good, albeit in many cases a small amount of bound water (between 0.5 and 2 molecules) are suggested. Recently, this issue has been addressed, and it is now unequivocally established that the dark product described is a Mn(III) oxygen adduct.¹⁷⁵ The precise nature of this adduct is less clear, with the authors suggesting it is monomeric, but a recent crystal structure (Fig. 15) has shown that (at least in part) it is a dimeric oxygen-bridged complex.¹⁷⁶

Fig. 15 Oxidation of [Mn(S₂CNR₂)₂] with proposed Mn(III) adducts and the molecular structure of [Mn₂(S₂CNEt₂)₄(μ-O₂)].^175,176

The colour of the oxygen adducts is very similar to that for Mn(III) complexes, [Mn(S₂CNR₂)₃], generated upon addition of three equivalents of dithiocarbamate to Mn(II) salts in air, as is the spectroscopic data. Thus, it is not easy to differentiate between the two. If two equivalents of dithiocarbamate are added to Mn(II) salts in water under argon then heavy yellow precipitates result, which are unequivocally [Mn(S₂CNR₂)₂]. Further, later exposure to oxygen (bubbling through solution works best to ensure full oxidation) reliably affords the pure oxygen adduct.¹⁷⁵ Addition of more dithiocarbamate salt to the latter gives [Mn(S₂CNR₂)₃], although it is hard to know exactly when the reaction is complete and to ensure that it is, a slight excess of dithiocarbamate is recommended.¹⁷⁵

Manganese dithiocarbamate complexes are becoming widely used as single source precursors (SSPs) to manganese sulfide nanomaterials.^177–180 In this respect, the accidental use of the oxygen adduct may be advantageous. Thus, oxygen adducts have a higher manganese content than [Mn(S₂CNR₂)₃] and, as shown by thermogravimetric analysis (TGA) for the diethyl derivatives (Fig. 16), decompose at lower temperatures. Indeed, TGA is a good way of differentiating between these two Mn(III) dithiocarbamate complexes.¹⁷⁶ Finally, we note that [Mn(S₂CNR₂)₃] decomposes in a two-step process, the former being associated with loss of a dithiocarbamate and in situ formation of [Mn(S₂CNR₂)₂], thus negating the need to isolate air sensitive Mn(II) complexes.

Fig. 16 TGA data for [Mn(S₂CNEt₂)₃] and [Mn₂(S₂CNEt₂)₄(μ-O₂)].¹⁷⁶

An early application of dithiocarbamates was as fungicides, with manganese containing Maneb© being widely used. It is formed from the reaction of Mn(II) salts with Nabam©, the bis(dithiocarbamate) generated from ethylene diamine (Fig. 17). More recently it has been linked to the development of Parkinson's disease^181,182 and since 2009 has been banned in the European Union, a fate also experienced by the zinc complex, Zineb©, which was also previously used as a pesticide.

Fig. 17 Formation of Nabem© and reaction with Mn(II) salts to produce Maneb©.

Maneb© and Zineb© were used in agriculture for many years and are proposed to have polymeric structures, as has the double hydration product of Maneb© namely [Mn(S₂CNHC₂H₄NHCS₂)·2H₂O]_n. Recently a good quality molecular structure of the dimethylformamide (dmf) adduct [Mn(S₂CNHC₂H₄NHCS₂)·2dmf]_n was reported¹⁸³ (Fig. 18) and confirms this. Manganese is in the +2 oxidation state but, importantly, has an octahedral coordination geometry with coordination of two cis dmf molecules (there are another two non-coordinated dmfs not shown). Likely hydrated Maneb© has a very similar structure except with bound water. Another interesting observation is that while pure samples of this adduct and Maneb© are yellow, the latter ages over time, becoming dark.

Fig. 18 Part of the polymeric structure of [Mn(S₂CNHC₂H₄NCS₂)·2dmf]_n.¹⁸³

(iv) [Fe(S₂CNR₂)₂]

Like their manganese counterparts, [Fe(S₂CNR₂)₂] can be prepared and isolated but are extremely air sensitive and should be handled in a dry box or a high quality Schlenk line environment. When prepared under the correct conditions they are described as chocolate brown,¹⁶² pink¹⁴² or red¹⁸⁴ solids. Crystal structures of two polymorphs of [Fe(S₂CNEt₂)₂]^185,186 show that it adopts a dimeric structure in the solid state (Fig. 19). Each iron centre is 5-coordinate, being best described as a distorted trigonal bipyramid. No other molecular structures have been determined, but there is some early evidence from Mössbauer studies that some derivatives may be coordination polymers.^187,188

Fig. 19 The molecular structure of [Fe(S₂CNEt₂)₂]₂.¹⁸⁵

As with the manganese chemistry described above, many authors describe the purported synthesis of Fe(II) bis(dithiocarbamate) complexes in air, and thus their assignment is clearly wrong. Unlike the manganese chemistry, however, it is less clear exactly what they have made if only two equivalents of dithiocarbamate are used. Thus, oxygen adducts of [Fe(S₂CNR₂)₂] have not been reported. These complexes do undergo rapid addition, for example addition of bis(perfluoromethyl)-1,2-dithietene affords Fe(III) complexes (Fig. 20) showing how prone they are to oxidation.¹⁸⁹ It is also known that [Fe(S₂CNR₂)₂] react with excess dithiocarbamate to afford yellow [Fe(S₂CNR₂)₃]⁻, which are also extremely air sensitive, being rapidly oxidised to brown Fe(III), [Fe(S₂CNR₂)₃].¹⁹⁰ Thus, it is most likely that reaction of two equivalents of dithiocarbamate with Fe(II) salts in air simply gives reduced yields of [Fe(S₂CNR₂)₃] along with some unreacted Fe(II) salt.

Fig. 20 Reactions of [Fe(S₂CNR₂)₂] with a dithietane resulting in oxidation, and addition of further dithiocarbamate followed by oxidation.

Bis(dithiocarbamate) complexes [Fe(S₂CNR₂)₂] also bind neutral donor ligands, as shown in crystal structures of a dmf adduct of the morpholine-dithiocarbamate complex (Fig. 21a)¹⁹¹ and a DABCO adduct of [Fe(S₂CNEt₂)₂] which co-crystallises with C₆₀ ¹⁴⁴ (Fig. 21b). Thus, from aqueous solutions, it may be that a species [Fe(S₂CNR₂)₂·H₂O] precipitates out. Interestingly, an NMR spectrum of [Fe(S₂CNC₄H₈O)₂·dmf] run in CDCl₃ was found to be identical to that of paramagnetic [Fe(S₂CNC₄H₈O)₃], suggesting oxidation and ligand arrangement upon dissolution in this weakly acidic solvent.¹⁹¹ Thus, it might be that Fe(II) is reducing enough to convert H⁺ into H₂ with concomitant formation of Fe(III).

Fig. 21 Molecular structure of (a) [Fe(S₂CNC₄H₈O)₂·dmf]¹⁹¹ and (b) [{Fe(S₂CNEt₂)₂}₂DABCO] as part of a large structure with C₆₀·2DABCO.¹⁴⁴

The Fe(II) oxidation state can be also stabilised by binding of carbonyls in cis-[Fe(CO)₂(S₂CNR₂)₂]^192,193 and NO in [Fe(NO)(S₂CNR₂)₂].^194,195 Indeed, the binding of NO to [Fe(S₂CNEt₂)₂], as determined by the distinctive EPR spectrum of [Fe(NO)(S₂CNEt₂)₂], is an accepted way of determining the presence of this important signalling gas.^196–198 It is noteworthy, however, that reaction of NO with [Fe(S₂CNEt₂)₃] also affords [Fe(NO)(S₂CNEt₂)₂] (together with thiuram disulfide as a byproduct).¹⁹⁸ Photolysis of [Fe(S₂CNEt₂)₃] also results in elimination of thiuram disulfide and formation of [Fe(S₂CNEt₂)₂], which can be trapped with bis(diphenylphosphino)ethane (dppe) to afford [Fe(κ²-dppe)(S₂CNEt₂)₂].¹⁹⁹ This suggests that there is a fine redox balance between the reducible Fe(III) centre and the oxidisable dithiocarbamate. Indeed, we have found using in situ EXAFS, that upon warming [Fe(S₂CNⁱBu₂)₃] in oleylamine at 60 °C, reductive elimination of thiuram disulfide results with concomitant formation of the corresponding Fe(II) complex.¹⁹³ Further, TGA measurements show that cis-[Fe(CO)₂(S₂CNR₂)₂] lose both carbonyls at relatively low temperatures to afford [Fe(S₂CNR₂)₂]. Thus, [Fe(S₂CNR₂)₂], [Fe(S₂CNR₂)₃] and cis-[Fe(CO)₂(S₂CNR₂)₂] are all effectively equivalents when used as SSPs¹⁹³ thus negating the need to isolate air sensitive [Fe(S₂CNR₂)₂].

Neither [M(S₂CNR₂)₂] (M = Ru, Os) appear in the reliable literature, with both metals favouring the M(III) state [M(S₂CNR₂)₃], but like iron, carbonyl-stabilised M(II) complexes cis-[Ru(CO)₂(S₂CNR₂)₂]²⁰⁰ and cis-[Os(CO)₂(S₂CNR₂)₂]^201–203 are accessible.

(v) [Co(S₂CNR₂)₂]

The theme continues into the chemistry of cobalt. Like iron and manganese, cobalt forms stable M(III) tris(dithiocarbamate) complexes [Co(S₂CNR₂)₃], the low spin d⁶ electronic configuration allowing NMR characterisation.^204–206 In contrast, while the corresponding M(II) species [Co(S₂CNR₂)₂] are accessible, they are extremely air-sensitive and paramagnetic, with [Co(S₂CNEt₂)₂] being described as a dark green-brown solid.¹⁴² It is telling that there are no crystal structures of [Co(S₂CNR₂)₂] and examples of authentic syntheses and characterisation are rare. Most authors report the formation of green precipitates from reactions of dithiocarbamate salts with CoCl₂·6H₂O in air, i.e. they actually generate [Co(S₂CNR₂)₃]. Recently, Khitrich and co-workers provided some evidence for the formation of [Co(S₂CNR₂)₂],²⁰⁷ suggesting that, provided pH is kept between 6–7, then even in air aqueous solutions of [CoCl₂] react with two equivalents of NaS₂CNR₂ to afford [Co(S₂CNR₂)₂] and note that in the solid state they are air stable. Good elemental analysis data are presented, and powder X-ray diffraction studies reveal (for those that are not amorphous) the absence of [Co(S₂CNR₂)₃]. Further, magnetic moments of 2.19–2.45 BM suggest that they have one unpaired electron, consistent with a square planar geometry. Interestingly, when dissolved in organic solvents they oxidise rapidly with formation of [Co(S₂CNR₂)₃] and [Co(OH)₂] (Fig. 22). Clearly more work in this area is warranted.

Fig. 22 Proposed decomposition of [Co(S₂CNR₂)₂] in organic solvents.²⁰⁷

Electrochemical reduction of [Co(S₂CNR₂)₃] leads to dithiocarbamate loss to give [Co(S₂CNR₂)₂], but back oxidation is facile.²⁰⁸ Chemical reduction of [Co(S₂CNR₂)₃] by excess Zn/Hg in CH₂Cl₂ results in a slow (ca. 3 h) darkening of the green solution and when canulated under nitrogen onto PhI = NTs, the Co(II) complexes react via insertion into the Co–S bonds to afford crystallographically characterised [Co{TsNSC(NR₂)SNTs}₂]²⁰⁹ (Fig. 23). Thus, it is chemically possible to prepare [Co(S₂CNR₂)₂] in organic solvents but oxygen must be rigorously excluded.

Fig. 23 Reductive generation of [Co(S₂CNR₂)₂] and trapping via multiple NTs insertion in the Co–S bonds.

We note that there are no authentic examples of [Rh(S₂CNR₂)₂] or [Ir(S₂CNR₂)₂] complexes,^210,211 all purported syntheses being likely that of the analogous [M(S₂CNR₂)₃] complexes.^212,213 Electrochemical reduction of [Rh(S₂CNR₂)₃] is irreversible and shown to be a two-electron process with formation of [Rh(S₂CNR₂)₂]⁻ and dithiocarbamate being suggested.²¹⁴

5. Structure and stability of dithiocarbamate complexes

(i) [M(S₂CNR₂)₂] (M = Mn, Fe, Co) are all square planar

In solution or the gas phase, the molecular structures of group 10 bis(dithiocarbamate) complexes and [Cu(S₂CNR₂)₂] are square planar. In the solid state, the 4-coordinate square planar arrangement is maintained for [M(S₂CNR₂)₂] (M = Ni, Pd, Pt), but the precise metal coordination environment for copper varies with substituents due to secondary Cu⋯S interactions.^8,13 The solution and gas phase structures of [M(S₂CNR₂)₂] (M = Mn, Fe, Co) remain unknown, although some authors suggest that all are square planar. This seems highly unlikely for [Mn(S₂CNR₂)₂] as for a d⁵ electronic conformation one would not expect the difference in crystal field stabilisation energies (CFSEs) between tetrahedral and square planar geometries to override steric effects, even when the preferred bite angle for dithiocarbamates is less than 90°. An early communication suggested that, in ethanol, [Mn(S₂CNEt₂)₂] adopts a spin quartet state, i.e. has 3 unpaired electrons,²¹⁵ although it was later shown that this result was erroneous, as measurements had been made on a partially oxidised sample. Upon rigorous exclusion of air, magnetic measurements on [Mn(S₂CNEt₂)₂] and other derivatives show that they adopt a ground state with 5 unpaired electrons.¹⁷² Thus, it seems likely that [Mn(S₂CNR₂)₂] have a distorted tetrahedral coordination geometry, although a recent DFT study suggests a square-planar arrangement, which may be a local minimum.²¹⁶ In a similar vein, iron complexes, [Fe(S₂CNR₂)₂], with a d⁶ electronic configuration have been shown to have 4 unpaired electrons,¹⁸⁶ being inconsistent with a square-planar array. Nevertheless, recent DFT calculations propose a local FeS₄ geometry with D_2h symmetry, consistent with a square planar geometry.²¹⁷ Clearly, accurate calculations are required to corroborate the actual coordination geometry. The absence of any crystallographic data makes it harder to predict the molecular geometry of d⁷ [Co(S₂CNR₂)₂], but they are likely square-planar, as supported by the magnetic susceptibility measurements and DFT calculations.²¹⁸

(ii) Ru(III) complexes [Ru(S₂CNR₂)₃] and [Ru(S₂CNHR)₃] are diamagnetic

Iron tris(dialkylDTC) complexes, [Fe(S₂CNR₂)₃], have been widely studied as spin crossover complexes as they can adopt either high spin (HS) ⁶A₁ or low spin (LS) ²T₂ electronic configurations, the position of the equilibrium being affected by the nature of the alkyl-substituents and external factors such as temperature and pressure.^219–222 Receiving less attention are analogous Ru(III) complexes, [Ru(S₂CNR₂)₃], although a number of early papers established their fluxional distorted octahedral structures²²³ and paramagnetic nature,^224,225 the latter being as expected for a d⁵ electronic configuration. Nevertheless, several publications claim to have prepared diamagnetic Ru(III) tris(dithiocarbamate) complexes of both secondary and primary amines, characterised by (almost perfect) elemental analysis data and ¹H NMR peaks in the standard 0–10 ppm range.^226–228 Interestingly, ¹H NMR spectroscopy can be used to part-characterise [Ru(S₂CNR₂)₃], although peaks are observed across a ca. 40 ppm range, as expected for a weak (low spin) paramagnetic system.^229–231 Diamagnetic complexes can be formed from the reaction of RuCl₃ and dithiocarbamates, indeed many studies have reported mixtures of paramagnetic [Ru(S₂CNR₂)₃] and diamagnetic [Ru₂(S₂CNR₂)₅]⁺ (which can exist in two isomeric forms) from these reactions.^229–232 Thus, it may be that such diamagnetic cations are the real products of the reactions described above.^226–228 Akin to their ruthenium analogues, osmium complexes, [Os(S₂CNR₂)₃], are also low spin d⁵ systems that show resonances across a wide chemical shift range in their ¹H NMR spectra and are easily oxidised.²³³

(iii) Stable dithiocarbamate complexes of high-valent metal oxides are always accessible

One of the major benefits of the dithiocarbamate ligand is its ability to stabilise metals in a wide range of oxidation states, being (in simple terms) attributed to the accessibility of dithiocarbamate and thioureide resonance forms. Thus, the former is a relatively soft (strong field) and the latter a hard (weak field) donor. While not unique to dithiocarbamates, some ligand sets, for example the related xanthates (ROCS₂⁻), cannot adopt the latter form as the oxygen is too electronegative to act as an electron-pair donor.²³⁴ Adoption of the thioureide form also accounts for the partial double bond character of the backbone C–N vector which leads to hindered rotation about it.²³⁵ Thus, rotamers of complexes [M(S₂CNR¹R²)₂] (M = Ni, Pd) can be distinguished, and their rate of interconversions measured.²³⁶ The thioureide form can also account for the stability of high-valent species such as of Mo(VI) and W(VI) complexes.^8,9 However, one should not forget that the dithiocarbamate is redox active, being relatively easily oxidised, and thus when bound to a highly oxidised metal centre, the system is on a cliff edge, as beautifully illustrated by a series of publications from Stiefel and co-workers.^237–241

While a wide range of metal centres and oxidation states can be tolerated by dithiocarbamates,⁸ this does not extend to the most oxidising. For example, reaction of dithiocarbamate salts with potassium dichromate, K₂[Cr₂O₇], affords a mixture of two Cr(III) products: ring-expanded [Cr(S₂CNR₂)₂(OS₂CNR₂)] as the major component together with [Cr(S₂CNR₂)₃] (R = Me, Et)²⁴² (Fig. 24). Thus, (at least formally) three equivalents of dithiocarbamate act as one-electron reducing agents and the other three as ligands. The precise mode of formation of the ring-expanded complex is not clear. In related work, Farmer and co-workers showed that addition of H₂O₂ to [Ru(κ²-2,2′-bipy)₂(S₂CNMe₂)]⁺ afforded both ring-expanded sulfur-oxidised isomers but they did not interconvert, suggesting that they are formed via two separate pathways,²⁴³ although in other work they showed that [Zn(S₂CNEt₂)(OS₂CNEt₂)] was a product of the oxygenation of [Zn(S₂CNEt₂)₂], a transformation that can be reversed upon addition of a phosphine.²⁴⁴ Interestingly, reaction of chromate with excess dithiocarbamate has been repurposed as an analytical method of measuring relative amounts of Cr(III) and Cr(IV).^245–247 Thus, Cr(III) reacts to form [Cr(S₂CNR₂)₃] and Cr(VI) a mixture of this and the ring-expanded products. Importantly the two products have different chromatographic retention times and thus by understanding the precise ratio of products formed from the Cr(VI) reaction it is possible to determine relative amounts of Cr(III) and Cr(VI), although not all publications seem to do it this way, with some suggesting that Cr(III) is unreactive towards dithiocarbamates.

Fig. 24 Cr(III) complexes from reaction of dithiocarbamates and K₂[Cr₂O₇].

Likely dithiocarbamates cannot stabilise high oxidation states such as Os(VIII) and Re(VII), since these metal centres are powerful oxidising agents. There are reports of Os(VI) dithiocarbamate complexes, trans-[OsO₂(S₂CNR₂)₂],^248,249 which show distinctive vibrations at 839 and 888 cm⁻¹ in the IR spectrum, being assigned to asymmetric and symmetric trans-OsO₂ vibrations respectively.²⁴⁹ Further investigations are needed to unequivocally establish the validity of these claims, but they seem quite likely to be correct given that the trans-[Os(VI)O₂] moiety is particularly stable, being found for example in complexes such as trans-[OsO₂(CO)₄]²⁺ and trans-[OsO₂(OH)₄]²⁻.

(iv) Au(III) complexes, [Au(S₂CNR₂)₂]⁺ and [AuCl₂(S₂CNR₂)], are easily prepared in their pure forms

Gold(III) dithiocarbamate complexes of the type [AuX₂(S₂CNR₂)] (where X = Cl, Br, I) have been widely studied as potential anti-cancer metallo-pharmaceuticals. Structurally they are comparable to cis-platin and the mechanism of action is suspected to be similar.²⁵⁰ These compounds were first synthesised in 1964 by oxidation of the Au(I) complex [Au(S₂CNR₂)]_n with elemental X₂.²⁵¹ This supposedly afforded the Au(III) dithiocarbamate [AuX₂(S₂CNR₂)] as a single compound in solution. Alternatively, the addition of one equivalent of dithiocarbamate to Au(III) halides is claimed to result in the sole formation of [AuX₂(S₂CNR₂)]. In a similar fashion, addition of two equivalents of dithiocarbamate to Au(III) halides supposedly resulted in the sole formation of the cationic complex [Au(S₂CNR₂)₂]⁺.⁹ Often in this system X⁻ is invoked as the counterion, but a haloaurate species is more likely to be present.

We recently investigated the [AuX₂(S₂CNR₂)] system thoroughly and discovered that the established reactivity is not correct.²⁵² The series of compounds [AuX₂(S₂CNR₂)] where X = halide cannot be isolated as a single species in solution; instead, they exist in an equilibrium with [Au(S₂CNR₂)₂][AuX₄] (Fig. 25). This equilibrium is present irrespective of the method of synthesis, or the ratio of dithiocarbamate to Au(III). A careful look at the older literature reveals that this equilibrium has always been present even though it had not previously been acknowledged. For example, the ¹H and ¹³C{¹H} NMR spectra of dibenzyl-dithiocarbamate- and methylsarcosine-dithiocarbamate-derived Au(III) complexes both clearly show the presence of two dithiocarbamate environments, one for the neutral species and one for the ion pair.^253,254 Mass spectrometry of [AuX₂(S₂CNR₂)] revealed that the cation [Au(S₂CNR₂)₂]⁺ was also present in the sample, although it was explained as decomposition in solution.²⁵⁵ A single crystal containing [AuCl₂(S₂CNiPr₂)], two [Au(S₂CNiPr₂)₂]⁺ cations and two [ClO₄]⁻ anions was obtained, showing that both components of the equilibrium were present in a single reaction mixture.²⁵⁶ Recently, it was shown that an equilibrium mixture where [Au(S₂CNiPr₂)₂][AuCl₄] was the majority product could be converted to a mixture where [AuCl₂(S₂CNiPr₂)] was the majority product by refluxing in acetone.²⁵⁷

Fig. 25 Equilibrium between [Au(S₂CNR₂)₂][AuCl₄] and [AuCl₂(S₂CNR₂)].

We note here that it is possible to obtain [Au(S₂CNR₂)₂]⁺ as a single species in solution, but the counterion must be chosen with care and haloaurate anions should be avoided. For example, use of a weakly coordinating anion such as [BF₄]⁻ led to the isolation of [Au(S₂CNR₂)₂][BF₄] which showed no sign of existing as an equilibrium, even upon standing in solution for several weeks. However, as soon as the anion was metathesized to [AuCl₄]⁻, the equilibrium restarted.²⁵² In a similar vein, it is possible to isolate [AuX₂(S₂CNR₂)] as a single pure product in solution by avoiding the use of halide ions: stable systems are known to exist for X = Me, C₆F₅, mesityl and thiolate, for example.^258–261

The above notwithstanding, it is possible to fractionally crystallise [AuX₂(S₂CNR₂)] as a single compound. The neutral species forms orange crystals (in contrast to the ion pair, which is yellow); these are indefinitely stable in the solid phase, but as soon as the crystals are dissolved in an organic solvent then the equilibration process resumes. Researchers are urged to be cautious here by not mistaking this for a single pure product in solution.²⁶¹ It is also noteworthy that elemental analysis is not a useful characterization technique since the two components of the equilibrium, namely [AuX₂(S₂CNR₂)] and [Au(S₂CNR₂)₂][AuX₄], have identical empirical formulae and cannot be used to distinguish the two isomers.²⁶²

(v) Primary amine-derived dithiocarbamate complexes are always stable

The majority of dithiocarbamate chemistry focuses on those derived from secondary amines. There are several reasons for this, one being their greater stability vs. those derived from primary amines. Thus, while all dithiocarbamates are unstable in acidic media, the relatively acidic nature of the unique proton in RNHCS₂⁻ also makes them prone to instability in basic media. Nevertheless, there are some relatively simple and highly reproducible syntheses of primary amine dithiocarbamate salts. Examples of these are group 10^263–265 and group 12^266–269 [M(S₂CNHR)₂] complexes, but also [Co(S₂CNHR)₃]^270,271 and ^99mTc complexes with radiopharmaceutical applications.^272–274 The authenticity of homoleptic primary amine dithiocarbamate complexes of other metals is far less certain and likely the majority are too unstable to be isolated.

Upon metal binding the acidity of the backbone proton is retained, its removal generating the dianionic dithiocarbimate (or imidomethanedithiolate) ligand, S₂C=NR²⁻. Such ligands form complexes with a wide range of metals,¹⁰³ being especially prevalent for Group 10 elements and when the substituent is strongly electron-withdrawing, for example aryl or cyanide. For Group 10 elements, as discussed earlier (Fig. 8), double deprotonation upon addition of a strong base of [M(S₂CNHAr)₂] and [M(S₂CNHR)₂] affords the corresponding dithiocarbimate dianions that, provided they are kept under anhydrous and oxygen-free conditions, have significant lifetimes and can be used to prepare functionalised dithiocarbamate derivatives. Stability of the dithiocarbimate complexes (presumably) results from delocalisation of the excess electron density into the vacant d-orbital. However, this is not the case for most other metals. For example, addition of base to Group 12 complexes [M(S₂CNHR)₂] and [M(S₂CNHAr)₂] (M = Zn, Cd) results in rapid decomposition to give ZnS or CdS nanomaterials.^266–268 Indeed, this is advantageous, as is the case for [Ni(S₂CNHR)₂]²⁷⁵ as they provide low temperature routes to these nanomaterials (Fig. 26).

Fig. 26 Base-induced decomposition of [M(S₂CNHR)₂] to afford RNCS and nanoscale metal sulfides.

For organic chemists reading this it may ring bells as the base-induced decomposition of primary amine dithiocarbamates to afford organic isothiocyanates is a well-developed preparative method.^276–278 Indeed, often a metal ion is added to facilitate the process. Thus, such complexes are not stable, certainly under basic conditions, rapidly decomposing to afford the isothiocyanate. Nevertheless, there are (purported) examples of [Fe(S₂CNHR)₃]^279,280 and [Cu(S₂CNHR)₂]^281–285 in the literature, some of the latter being touted as enzyme inhibitors.²⁸⁵ We have recently looked more closely at both systems in our laboratory and will publish our results in due course. The iron system is complex and is not appropriate to discuss here, but [Fe(S₂CNHR)₃] have at best a fleeting stability. Reactions of copper(II) salts with a range of primary amine derived dithiocarbamates in water leads to isolation of high yields of bright yellow polymeric Cu(I) complexes, [Cu(S₂CNHR)]_n (R = Bu, Cy) along with the corresponding thiourea.²⁸⁶ Their poor solubility hinders full characterisation, but simple addition of a slight excess of PPh₃ affords the soluble and crystallographically characterised complexes, [Cu(S₂CNHR)(PPh₃)₂]²⁸⁶ (Fig. 27). In this regard we note that [Cu(S₂CNHPh)(PPh₃)₂] has previously been prepared from reaction of [Cu(BH₄)(PPh₃)₂] with PhNCS.²⁸⁷ Thus, primary amine dithiocarbamates are stable at a Cu(I) centre but not Cu(II).

Fig. 27 Formation of [Cu(S₂CNHR)]_n and subsequent reaction with PPh₃.

We briefly note here that [NH₄][S₂CNH₂] is easily prepared^288,289 and has been used to generate a range of stable homoleptic complexes, including crystallographically characterised: [Ni(S₂CNH₂)₂],²⁹⁰ [Zn(S₂CNH₂)₂],²⁹¹ [Cr(S₂CNH₂)₃],²⁹² [Co(S₂CNH₂)₃],^288,293 [Rh(S₂CNH₂)₃],²⁸⁸ [Ag(S₂CNH₂)],²⁹⁴ [Au(S₂CNH₂)],²⁹⁵ [Au(S₂CNH₂)₂][SCN],²⁹⁶ [Cu(S₂CNH₂)]²⁹⁷ and [Cu(S₂CNH₂)₂][NH₄].²⁹⁷ Considering the discussion above, the finding that this ligand is only stabilised at the Cu(I) centre is interesting. Further several non-homoleptic Ru(II) derivatives have been prepared and crystallographically characterised²⁸⁸ suggesting that there is a relatively rich coordination chemistry of this ligand still to be explored.

(v) Complexes with two different dithiocarbamate ligands and dithiocarbamate-containing mixed-ligand complexes are (easily) accessible in a pure state

Many homoleptic dithiocarbamate complexes are known, being easy to prepare even in the most basic of laboratory settings.^8,9 In developing this chemistry further, it is tempting to consider preparing related complexes in which two (or more) different dithiocarbamates bind to a single metal centre, thus providing easy tuning of chemical and physiochemical properties. Consequently, over the past decade, there has been an increasing number of publications claiming the formation of pure complexes containing two different dithiocarbamate ligands of Ni(II),²⁹⁸ Cu(II),^299–301 zinc and mercury^302–306 and other transition metal^307–309 and main group^310–315 elements. In all these reports, the simple addition of equimolar equivalents of two different dithiocarbamates to a metal salt is reported to (cleanly) afford the mixed-ligand complex, without any explanation as to why a mixed-ligand complex might be thermodynamically preferable to either the two homoleptic complexes or a statistical mixture of homo- and heteroleptic complexes. Very few of these reports are supported with single crystal X-ray data, or compelling characterising data. Crystal structures of [Hg(S₂CNMePh)(S₂CNEtPh)]³⁰⁴ and [Zn(S₂CNMePh)(S₂CNEtPh)(2,2′-bipy)]³⁰⁵ are in the literature but in both there is a significant disorder of the Me/Et groups. The only good quality (non-disordered) example of a molecular structure of a heteroleptic dithiocarbamate complex is that of the anion [Cd(S₂CNPr₂)₂(S₂CNMeBu)]⁻, formed (in a similar manner to other examples) upon addition of pyrrolidinium salts of [S₂CNMeBu]⁻ to [Cd(S₂CNPr₂)₂].³¹⁶ However, while the crystal structure shows a well-ordered mixed-dithiocarbamate complex, both ¹H and ¹³C{¹H} NMR spectra show that in solution multiple products are present, resulting from ligand-exchange. Thus, while complexes with two different dithiocarbamates are accessible as part of a mixture and can (at least potentially) be selectively crystallised out, they are not accessible in pure form in solution.

For diamagnetic species, NMR spectroscopy should be a simple way of probing such equilibria, however, the (relatively) slow timescale coupled with low intensity of the quaternary backbone carbon signal in the ¹³C{¹H} NMR spectrum and its insensitivity to substituent changes³¹⁷ renders it unsuitable. In contrast, HPLC has been shown to be an excellent analytical tool for investigating these systems, being used effectively, for example, by Moriyasu and Hashimoto,^318–320 Liska and co-workers^321,322 and others.³²³ Thus, Moriyasu and Hashimoto mixed homoleptic bis(dithiocarbamate) complexes of nickel and copper (which can't easily be studied by NMR spectroscopy) and in all cases found that they were labile and in equilibrium with the mixed-ligand counterpart (Fig. 28). Rate constants depend on both metal and substituents, for Ni(II) being of the order of 10¹–10² M⁻¹ s⁻¹ and for Cu(II) slower at ca. 10³ M⁻¹ s⁻¹.^317–320 These studies were later extended to other metals and in all cases, the dithiocarbamates were found to be labile with equilibrium constants being ca. 4, i.e. a statistical mixture of the three complexes.³²⁴ Similar equilibria have also been noted between homoleptic nickel complexes of primary and secondary amines, affording [Ni(S₂CNR¹₂)(S₂CNHR²)],^318–320 and also between [Ni(S₂CNR₂)₂] and xanthate complexes, [Ni(S₂COR)₂].³²⁵ Most studies support a bimolecular exchange process likely proceeding through a dimeric intermediate, the form of which is common in crystallographic studies of [Zn(S₂CNR₂)₂] and [Cu(S₂CNR₂)₂].⁸ Rapid dithiocarbamate exchange has also been noted at Fe(III)^326–328 and Hg(II)^329,330 centres.

Fig. 28 Equilibrium between homoleptic and mixed ligand bis(dithiocarbamate) complexes.

For low spin d⁶ [Co(S₂CNR₂)₃] complexes, the CFSE is so high that exchange rates are slow³³¹ and isolation of mixed-ligand complexes is possible. Thus, addition of a dithiocarbamate salt, NaS₂CNR¹₂ to [Co₂(S₂CNR²₂)₅]⁺ affords a mixture of [Co(S₂CNR¹₂)(S₂CNR²₂)₂] and [Co₂(S₂CNR²₂)₃]³³² (Fig. 29). Further, adding equimolar amounts of two different dithiocarbamates to Co(III) salts in water affords a statistical mixture of products,³³³ and a similar mixture of products can be obtained upon heating equimolar amounts of [Co(S₂CNEt₂)₃] and [Co(S₂CNⁱPr₂)₃] either in the solid-state or at 155 °C in chloronaphthalene for 4–5 h.³³³ Importantly, these mixtures can be fully separated by column chromatography allowing their individual characterisation. Interestingly, while it is hard to differentiate them by ¹H or ¹³C{¹H} NMR spectroscopy, they can be distinguished by ⁵⁹Co NMR spectroscopy and mass spectrometry and have tuneable oxidation potentials.³³³

Fig. 29 Synthesis of heteroleptic Co(III) dithiocarbamate complexes.

The ease of accessibility of mixed-ligand complexes containing dithiocarbamates also needs some careful consideration. There are many such examples^8,9 but for solution stability in their pure form they need to feature either a relatively non-labile metal centre with either bulky non-dithiocarbamate ligands that preclude formation of a bimetallic intermediate or secondary inter-ligand interactions (e.g. hydrogen-bonding). Following on from the discussion above, Co(III) is a good example of a non-labile metal centre. Thus, [Co₂(S₂CNR₂)₅]⁺ reacts with a range of nucleophiles to afford [Co(S₂CNR₂)₃] and a mixed-ligand complex, a recent case being the formation of Co(III) bis(dithiocarbamate)dithiolane complexes from addition of dithiones (Fig. 29).³³⁴ Other examples of a high CFSE leading to stable mixed-ligand complexes relate to the iron dithietane complexes¹⁸⁹ (Fig. 20) which exist in temperature-dependent spin-equilibrium between the singlet (S = 0) ground state and a low-lying triplet (S = 1) excited state. Thus, not only are these mixed-ligand complexes stable, but their NMR spectra are also accessible.

However, simultaneously adding a dithiocarbamate and a different ligand to a metal salt will not automatically afford the mixed-ligand species as has been suggested in several publications.^335–338 Just as for complexes with two different dithiocarbamates, it is hard by simple spectroscopic methods to tell the difference between a 1 : 1 mixture of two homoleptic complexes and a mixed-ligand species, and in many cases the three likely co-exist. A recent publication highlights this nicely (Fig. 30).³³⁹ Thus, while insertion of an imide group into a Ni–S bond of [Ni(S₂CNR₂)₂] affords mixed-ligand complexes, examples of which can be crystallographically characterised, upon dissolution they are shown to be in equilibrium with the two homoleptic complexes.

Fig. 30 Formation of mixed-ligand complex in equilibrium with homoleptic complexes.

(vi) Reacting two different dithiocarbamate complexes gives a pure mixed metal product

Given the extremely large number of homonuclear transition metal dithiocarbamate complexes that are known, it is perhaps surprising that dithiocarbamate-bridged heteronuclear complexes are rare. Thus, as shown by Robinson,³⁴⁰ complexes obtained by successive addition of metal salts MX₂ (M = Zn, Cd or Hg) and M′Y₂ (M′ = VO, Mn, Fe, Co, Ni, Cu or Zn) to a solution of a sodium dithiocarbamate are not heterobimetallic [{M′M(S₂CNR₂)₄}_n] but rather contain a mixture of homonuclear complexes. Likewise, reactions of Pd(II) salts [PdCl₂L₂] (L = PhCN, L₂ = dppe) with a series of homoleptic dithiocarbamate complexes affords palladium-dithiocarbamate cations [Pd(S₂CNR₂)L₂]⁺ with the second metal being incorporated into the counterion.^341–343 More recently, Torimoto and co-workers added Na(S₂CNEt₂) to mixtures of metal salts and used the ensuing “complex” as a precursor to a range of nanoscale metal sulfides with quantum dot properties.^344–347 While the method is effective and efficient, the suggestion that a mixed-metal complex is formed is erroneous. Rather the precursor “complex” is an intimate mixture of several different complexes. There are some well-authenticated examples of dithiocarbamate-bridged heterobimetallic complexes, being especially prevalent amongst the coinage metals^348–351 and there are also a small number of other dithiocarbamate-containing heteronuclear complexes that have been crystallographically characterised.^352,353 Nevertheless, the vast majority of dithiocarbamate complexes contain a single metal type.

6. Dithiocarbamate complexes as single source precursors

Dithiocarbamate complexes find widespread use as single source precursors for a range of nanoscale and thin film metal sulfides.^49–52 Thus, simply heating, either in the solid-state or solution, the complex or mixture of complexes, results in S–C and other bond scission(s) affording the thermodynamically stable metal-sulfide(s) and various organic species, the latter (normally) being easily removed either by washing or evaporation. The utility of this simple approach is that air-stable dithiocarbamate complexes from across the periodic table can be (relatively easily) prepared and stored, and by judicious control of reaction conditions and stoichiometry a wide range of binary, ternary and quaternary metal sulfides can be accessed. A nice example of this is their use towards the synthesis of Cu₂ZnSnS₄ (CZTS) a quaternary semiconductor with a power conversion efficiency of ca. 10% that has been suggested as a viable material for thin film solar cells. Thus, decomposing mixtures of copper, zinc and tin dithiocarbamates leads to the formation of CZTS thin films or quantum dots.^354,355

However, such transformations are not as simple as they might appear. Firstly, in the solid state, thermogravimetric analysis studies have shown that temperatures of between 200–400 °C are required to cleave the S–C (and other) bonds within dithiocarbamate complexes.^356–359 Decomposition temperatures can be tuned (normally within a small range) upon changing substituents, and there is also a correlation between the ease of thermal decomposition and ionic radius of the metal ion; the smaller the metallic ionic radius, the greater the thermal stability.³⁶⁰ In solution, decomposition temperatures can be significantly lower than in the solid-state.^275,361,362 For example, the water-soluble SSP [Cu{S₂CN(CH₂CO₂H)₂}₂] decomposes at 180 °C in the solid state but at ca. 80 °C in water.³⁶² Another issue to address when preparing ternary, quaternary or multinary sulfides, is matching of decomposition temperatures, such that all SSPs decompose within a relatively small range, thus ensuring that the different molecular building blocks are all available at the nucleation stage. This is nicely exemplified by O'Brien's synthesis of CZTS.^363,364 Thus, as the decomposition temperature of [Sn(S₂CNEt₂)₂] (174 °C) is significantly lower than those of [Cu(S₂CNEt₂)₂] (220 °C) and [Zn(S₂CNEt₂)₂] (240 °C), heating this mixture will lead to the premature formation of tin sulfides and hence the tin precursors was replaced by the Sn(IV) SSPs, [Sn(S₂CNBu₂)₄]³⁶³ and [Bu₂Sn(S₂CNBu₂)₂]³⁶⁴ which decompose at higher temperatures. A study by Torimoto and co-workers nicely highlights the need to carefully control decomposition conditions.³⁶⁵ Thus, for the synthesis of Ag(In_xGa_1−x)S₂ quantum dots, simply heating a mixture of silver, indium and gallium precursors initially results in formation of polydisperse Ag₂S as the silver dithiocarbamate decomposes at lower temperatures than others, and upon further heating as indium and gallium SSPs decompose they give a shell of these sulfides around the Ag₂S (Fig. 31a).³⁶⁶ However, when a silver source is injected into the decomposition reaction then co-nucleation of all components occurs, initially to give a core–shell structure, while further heating affords the desired ternary phase sulfide as quantum dots.³⁶⁵

Fig. 31 Schematic illustrations of the synthesis of Ag(In_xGa_1−x)S₂ quantum dots form (a) heating of the precursor mixture and (b) injecting a silver source into the decomposition mixture.³⁶⁵

Given these complications and constraints, it is surprising that there are an increasing number of reports seemingly suggesting that simply preparing mixtures of dithiocarbamates at room temperature results in the formation of metal sulfides i.e. there is no mention of a heating or other decomposition process^367–371 although decomposition appears to be supported by powder X-ray diffraction data. Further, many of these “decompositions” are proposed to give composite mixtures of individual metal sulfides, some of which such as BaS₃, are normally prepared at 400 °C.³⁷² Clearly such reports require some scrutiny and perhaps further explanation(s) from the authors.

7. Summary and conclusions

In this perspective we have tried to address common misconceptions and errors that we have found in the literature on dithiocarbamates and their complexes. Amongst the challenges faced by those working in this area are the vast number of publications and patents, and the widespread reach of this simple ligand type across many different fields of research. Thus, it is hard for anyone to fully keep up to date and understand all aspects of their chemistry. Likely many misconceptions-errors that have crept into the literature result are further exacerbated by the recent (seemingly unstoppable) proliferation of scientific journals. It is a testament to the wide applicability of dithiocarbamate chemistry that this perspective cites over 200 different journal titles: some of us long for the days when our library reading covered 10–15 journals, each with a clear remit. Thus, we need to understand that newcomers to this mature field of research have a lot of reading and understanding to do to get up to speed with what has gone before. Dithiocarbamate chemistry has been an active area of research for over 150 years and unlike some fields of scientific research, some early papers have relevance today. For example, while recently developing a primary-amine derived dithiocarbamate as a H₂S release-vector we came across a paper from 1891³⁷³ which had effectively already studied this and provided us with invaluable insight into our work.

Having said this, there is also some evidence of tardy work in the dithiocarbamate literature, with researchers either cutting corners, or not being totally honest in reporting their findings-data. Sadly, this appears to be an issue that has proliferated through all aspects of scientific research and one that seriously undermines the efforts of those who play fair. It is hard to understand why anyone would deliberately mis-represent their work, but undoubtably the high speed of modern living and (sometimes) excessive pressures put on academics to publish may be part of the problem. Linking publication to financial gain or making it a pre-requisite for promotion will tempt some to cut corners.

Conflicts of interest

There are no conflicts to declare.

Data availability

There is no data associated with this submission.

Acknowledgements

We thank Dr Jagodish C. Sarker for reading through the manuscript and providing valuable comments, and Dr Shishir Ghosh for attempting to reproduce a reaction discussed herein.

References

1. C. Campanale, M. Triozzi, A. Ragonese, D. Losacco and C. Massarelli, Dithiocarbamates: Properties, Methodological Approaches and Challenges to Their Control, Toxics, 2023, 11, 851.
2. J. M. Veiga-del-Bano, S. Martinez-Lopez, G. Perez-Lucas, J. J. Cuenca-Martinez and P. Andreo-Martinez, Trends in dithiocarbamates food research: A bibliometric vision, Chemosphere, 2023, 313, 137342.
3. R. J. Magee and J. O. Hill, The analytical chemistry of metal dithiocarbamate complexes, Rev. Anal. Chem., 1985, 8, 5–72.
4. L. Ye, A. T. Dinkova-Kostova, K. L. Wade, Y. Zhang, T. A. Shapiro and P. Talalay, Quantitative determination of dithiocarbamates in human plasma, serum, erythrocytes and urine: pharmacokinetics of broccoli sprout isothiocyanates in humans, Clin. Chim. Acta, 2002, 316, 43–53.
5. K. W. Bruland, R. P. Franks, G. A. Knauer and J. H. Martin, Sampling and analytical methods for the determination of copper, cadmium, zinc, and nickel at the nanogram per liter level in sea water, Anal. Chim. Acta, 1979, 105, 233–245.
6. C. Yuan, B. Liu, F. Liu, M.-Y. Han and Z. Zhang, Fluorescence “Turn On” Detection of Mercuric Ion Based on Bis(dithiocarbamato)copper(II) Complex Functionalized Carbon Nanodots, Anal. Chem., 2014, 86, 1123–1130.
7. O. H. J. Szolar, Environmental and pharmaceutical analysis of dithiocarbamates, Anal. Chim. Acta, 2007, 582, 191–200.
8. G. Hogarth, Transition metal dithiocarbamates: 1978–2003, Prog. Inorg. Chem., 2005, 53, 71–561.
9. D. Coucouvanis, The chemistry of the dithioacid and 1,1-dithiolate complexes, 1968–1977, Prog. Inorg. Chem., 1979, 26, 301–469.
10. P. J. Heard, Main group dithiocarbamate complexes, Prog. Inorg. Chem., 2005, 53, 1–69.
11. F. Bonati and R. Ugo, Organotin(IV) N,N-disubstituted dithiocarbamates, J. Organomet. Chem., 1967, 10, 257–268.
12. E. R. T. Tiekink, Tin dithiocarbamates: applications and structures, Appl. Organomet. Chem., 2008, 22, 533–550.
13. G. Hogarth and D. C. Onwudiwe, Copper Dithiocarbamates: Coordination Chemistry and Applications in Materials Science, Biosciences and Beyond, Inorganics, 2021, 9, 70.
14. A. M. Bond and R. L. Martin, Electrochemistry and redox behavior of transition metal dithiocarbamates, Coord. Chem. Rev., 1984, 54, 23–98.
15. Y. S. Tan, C. I. Yeo, E. R. T. Tiekink and P. J. Heard, Dithiocarbamate Complexes of Platinum Group Metals: Structural Aspects and Applications, Inorganics, 2021, 9, 60.
16. J. Cookson and P. D. Beer, Exploiting the dithiocarbamate ligand in metal-directed self-assembly, Dalton Trans., 2007, 1459–1472.
17. A. Torres-Huerta, B. Rodriguez-Molina, H. Hopfl and M. A. Garcia-Garibay, Synthesis and Solid-State Characterization of Self-Assembled Macrocyclic Molecular Rotors of Bis(dithiocarbamate) Ligands with Diorganotin(IV), Organometallics, 2014, 33, 354–362.
18. E. R. T. Tiekink, On the coordination role of pyridyl-nitrogen in the structural chemistry of pyridyl-substituted dithiocarbamate ligands, Crystals, 2021, 11, 286.
19. L. Monser and N. Adhoum, Modified activated carbon for the removal of copper, zinc, chromium and cyanide from wastewater, Sep. Purif. Technol., 2002, 26, 137–146.
20. M. Tuzen, K. O. Saygi and M. Soylak, Solid phase extraction of heavy metal ions in environmental samples on multiwalled carbon nanotubes, J. Hazard. Mater., 2008, 152, 632–639.
21. P. I. Girginova, A. L. Daniel-da-Silva, C. B. Lopes, P. Figueira, M. Otero, V. S. Amaral, E. Pereira and T. Trindade, Silica coated magnetite particles for magnetic removal of Hg²⁺ from water, J. Colloid Interface Sci., 2010, 345, 234–240.
22. S. Kanchi, P. Singh and K. Bisetty, Dithiocarbamates as hazardous remediation agent: A critical review on progress in environmental chemistry for inorganic species studies of 20^th century, Arabian J. Chem., 2014, 7, 11–25.
23. K. Nakakubo, M. Endo, Y. Sakai, F. B. Biswas, K. H. Wong, A. S. Mashio, T. Taniguchi, T. Nishimura, M. Katsuhiro and H. Hasegawa, Crosslinked dithiocarbamate-modified cellulose with enhanced thermal stability and dispersibility as a sorbent for arsenite removal, Chemosphere, 2022, 307, 135671.
24. G. Hogarth, Metal-dithiocarbamate complexes: chemistry and biological activity, Mini-Rev. Med. Chem., 2012, 12, 1202–1215.
25. C. Nardon, G. Boscutti and D. Fregona, Beyond platinums: gold complexes as anticancer agents, Anticancer Res., 2014, 34, 487–492.
26. L. Ronconi, L. Giovagnini, C. Marzano, F. Bettio, R. Graziani, G. Pilloni and D. Fregona, Gold Dithiocarbamate Derivatives as Potential Antineoplastic Agents: Design, Spectroscopic Properties, and in Vitro Antitumor Activity, Inorg. Chem., 2005, 44, 1867–1881.
27. L. Ronconi, C. Marzano, P. Zanello, M. Corsini, G. Miolo, C. Macca, A. Trevisan and D. Fregona, Gold(III) Dithiocarbamate Derivatives for the Treatment of Cancer: Solution Chemistry, DNA Binding, and Hemolytic Properties, J. Med. Chem., 2006, 49, 1648–1657.
28. F. K. Keter, I. A. Guzei, M. Nell, W. E. van Zyl and J. Darkwa, Phosphinogold(I) Dithiocarbamate Complexes: Effect of the Nature of Phosphine Ligand on Anticancer Properties, Inorg. Chem., 2014, 53, 2058–2067.
29. J. O. Adeyemi and D. C. Onwudiwe, Organotin(IV) dithiocarbamate complexes: chemistry and biological activity, Molecules, 2018, 23, 1–27.
30. R. Schreck, B. Meier, D. N. Maennel, W. Droege and P. A. Baeuerle, Dithiocarbamates as potent inhibitors of nuclear factor κB activation in intact cells, J. Exp. Med., 1992, 175, 1181–1194.
31. Q. W. Xie, Y. Kashiwabara and C. Nathan, Role of transcription factor NF-κB/Rel in induction of nitric oxide synthase, J. Biol. Chem., 1994, 269, 4705–4708.
32. M. Meyer, R. Schreck and P. A. Baeuerle, Hydrogen peroxide and antioxidants have opposite effects on activation of NF-κB and AP-1 in intact cells: AP-1 as secondary antioxidant-responsive factor, EMBO J., 1993, 12, 2005–2015.
33. N. Marui, M. K. Offermann, R. Swerlick, C. Kunsch, C. A. Rosene, M. Ahmad, R. W. Alexander and R. M. Medford, Vascular cell adhesion molecule-1 (VCAM-1) gene transcription and expression are regulated through an antioxidant-sensitive mechanism in human vascular endothelial cells, J. Clin. Inhib. Med. Chem., 1993, 92, 1866–1874.
34. C. T. Supuran, Structure-based drug discovery of carbonic anhydrase inhibitors, J. Enzyme Inhib. Med. Chem., 2012, 27, 759–772.
35. F. Carta, M. Aggarwal, A. Maresca, A. Scozzafava, R. McKenna and C. T. Supuran, Dithiocarbamates: a new class of carbonic anhydrase inhibitors. Crystallographic and kinetic investigations, Chem. Commun., 2012, 48, 1868–1870.
36. F. Carta, M. Aggarwal, A. Maresca, A. Scozzafava, R. McKenna, E. Masini and C. T. Supuran, Dithiocarbamates strongly inhibit carbonic anhydrases and show antiglaucoma action in vivo, J. Med. Chem., 2012, 55, 1721–1730.
37. D. J. Berry, R. T. Martin de Rosales, P. Charoenphun and P. J. Blower, Dithiocarbamate complexes as radiopharmaceuticals for medical imaging, Mini-Rev. Med. Chem., 2012, 12, 1174–1183.
38. R. Pasqualini, A. Duatti, E. Bellande, V. Comazzi, V. Brucato, D. Hoffschir, D. Fagret and M. Comet, Bis(dithiocarbamato) nitrido technetium-99 m radiopharmaceuticals: a class of neutral myocardial imaging agents, J. Nucl. Med., 1994, 35, 334–341.
39. R. T. Martin de Rosales, R. Tavare, R. L. Paul, M. Jauregui-Osoro, A. Protti, A. Glaria, G. Varma, I. Szanda and P. J. Blower, Synthesis of ⁶⁴CuII-Bis(dithiocarbamatebisphosphonate) and Its Conjugation with Superparamagnetic Iron Oxide Nanoparticles: In Vivo Evaluation as Dual-Modality PET-MRI Agent, Angew. Chem., Int. Ed., 2011, 50, 5509–5513.
40. R. T. A. Mayadunne, E. Rizzardo, J. Chiefari, Y. K. Chong, G. Moad and S. H. Thang, Living Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization) Using Dithiocarbamates as Chain Transfer Agents, Macromolecules, 1999, 32, 6977–6980.
41. G. Moad, E. Rizzardo and S. H. Thang, Radical addition-fragmentation chemistry in polymer synthesis, Polymer, 2008, 49, 1079–1131.
42. M. Destarac, D. Charmot, X. Franck and S. Z. Zard, Dithiocarbamates as universal reversible addition-fragmentation chain transfer agents, Macromol. Rapid Commun., 2000, 21, 1035–1039.
43. G. Moad, A Critical Survey of Dithiocarbamate Reversible Addition-Fragmentation Chain Transfer (RAFT) Agents in Radical Polymerization, J. Polym. Sci., Part A: Polym. Chem., 2019, 57, 216–227.
44. Y. Zhao, W. Perez-Segarra, Q. Shi and A. Wei, Dithiocarbamate Assembly on Gold, J. Am. Chem. Soc., 2005, 127, 7328–7329.
45. C. M. Wolff, P. D. Frischmann, M. Schulze, B. J. Bohn, R. Wein, P. Livadas, M. T. Carlson, F. Jaeckel, J. Feldmann and F. Wuerthner, et al., All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods, Nat. Energy, 2018, 3, 862–869.
46. F. Dubois, B. Mahler, B. Dubertret, E. Doris and C. Mioskowski, A Versatile Strategy for Quantum Dot Ligand Exchange, J. Am. Chem. Soc., 2007, 129, 482–483.
47. E. R. Knight, A. R. Cowley, G. Hogarth and J. D. E. T. Wilton-Ely, Bifunctional dithiocarbamates: a bridge between coordination chemistry and nanoscale materials, Dalton Trans., 2009, 607–609.
48. J. He, J. Liu, Y. Hou, Y. Wang, S. Yang and H. G. Yang, Surface chelation of caesium halide perovskite by dithiocarbamate for efficient and stable solar cells, Nat. Commun., 2020, 11, 4237.
49. J. C. Sarker and G. Hogarth, Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides, Chem. Rev., 2021, 121, 6057–6123.
50. D. Pan, L. An, Z. Sun, W. Hou, Y. Yang, Z. Yang and Y. Lu, Synthesis of Cu-In-S Ternary Nanocrystals with Tuneable Structure and Composition, J. Am. Chem. Soc., 2008, 130, 5620–5621.
51. M. A. Malik, N. Revaprasadu and P. O'Brien, Air-Stable Single-Source Precursors for the Synthesis of Chalcogenide Semiconductor Nanoparticles, Chem. Mater., 2001, 13, 913–920.
52. T. Trindade, P. O'Brien, X.-M. Zhang and M. Motevalli, Synthesis of PbS nanocrystallites using a novel single molecule precursors approach: X-ray single-crystal structure of Pb(S₂CNEt-iso-Pr)₂, J. Mater. Chem., 1997, 7, 1011–1016.
53. P. Tsvetkov, S. Coy, B. Petrova, M. Dreishpoon, A. Verma, M. Abdusamad, J. Rossen, L. Joesch-Cohen, R. Humeidi, R. D. Spangler, J. K. Eaton, E. Frenkel, M. Kocak, S. M. Corsello, S. Lutsenko, N. Kanarek, S. Santagata and T. R. Golub, Copper induces cell death by targeting lipoylated TCA cycle proteins, Science, 2022, 375, 1254–1261.
54. D. Chen, Q. C. Cui, H. Yang and Q. P. Dou, Disulfiram, a Clinically Used Anti-Alcoholism Drug and Copper-Binding Agent, Induces Apoptotic Cell Death in Breast Cancer Cultures and Xenografts via Inhibition of the Proteasome Activity, Cancer Res., 2006, 66, 10425–10433.
55. D. Cen, D. Brayton, B. Shahandeh, F. L. Meyskens Jr. and P. J. Farmer, Disulfiram Facilitates Intracellular Cu Uptake and Induces Apoptosis in Human Melanoma Cells, J. Med. Chem., 2004, 47, 6914–6920.
56. D. J. Lewis, P. Deshmukh, A. A. Tedstone, F. Tuna and P. O'Brien, On the interaction of copper(II) with disulfiram, Chem. Commun., 2014, 50, 13334–13337.
57. B. Cvek, V. Milacic, J. Taraba and Q. P. Dou, Ni(II), Cu(II), and Zn(II) Diethyldithiocarbamate Complexes Show Various Activities Against the Proteasome in Breast Cancer Cells, J. Med. Chem., 2008, 51, 6256–6258.
58. Z. Skrott, M. Mistrik, K. K. Andersen, S. Friis, D. Majera, J. Gursky, T. Ozdian, J. Bartkova, Z. Turi, P. Moudry, I. Vrobel, P. Pouckova, J. Sedlacek, A. Miklovicova, A. Kutt, J. Li, J. Mattova, C. Driessen, Q. P. Dou, J. Olsen, M. Hajduch, B. Cvek, R. J. Deshaies and J. Bartek, Alcohol-abuse drug disulfiram targets cancer via p97 segregase adaptor NPL4, Nature, 2017, 552, 194–199.
59. Z. Skrott and B. Cvek, Diethyldithiocarbamate complex with copper: the mechanism of action in cancer cells, Mini-Rev. Med. Chem., 2012, 12, 1184–1192.
60. E. J. Ge, A. I. Bush, A. Casini, P. A. Cobine, J. R. Cross, G. M. DeNicola, Q. P. Dou, K. J. Franz, V. M. Gohil, S. Gupta, S. G. Kaler, S. Lutsenko, V. Mittal, M. J. Petris, R. Polishchuk, M. Ralle, M. L. Schilsky, N. K. Tonks, L. T. Vahdat, L. Van Aelst, D. Xi, P. Yuan, D. C. Brady and C. J. Chang, Connecting copper and cancer: from transition metal signalling to metalloplasia, Nat. Cancer Rev., 2022, 22, 102–113.
61. E. Ekinci, S. Rohondia, R. Khan and Q. P. Dou, Repurposing Disulfiram as An Anti-Cancer Agent: Updated Review on Literature and Patents, Recent Pat. Anti-Cancer Drug Discovery, 2019, 14, 113–132.
62. Q. Yang, Y. Yao, K. Li, L. Jiao, J. Zhu, C. Ni, M. Li, Q. P. Dou and H. Yang, An Updated Review of Disulfiram: Molecular Targets and Strategies for Cancer Treatment, Curr. Pharm. Des., 2019, 25, 3248–3256.
63. X. Kang, S. Jadhav, M. Annaji, C.-H. Huang, R. Amin, J. Shen, C. R. Ashby Jr., A. K. Tiwari, R. J. Babu and P. Chen, Advancing Cancer Therapy with Copper/Disulfiram Nanomedicines and Drug Delivery Systems, Pharmaceutics, 2023, 15, 1567.
64. Z. Skrott, D. Majera, J. Gursky, T. Buchtova, M. Hajduch, M. Mistrik and J. Bartek, Disulfiram's anti-cancer activity reflects targeting NPL4, not inhibition of aldehyde dehydrogenase, Oncogene, 2019, 38, 6711–6722.
65. C. Wright and R. D. Moore, Disulfiram treatment of alcoholism, Am. J. Med., 1990, 88, 647–655.
66. J. Cobby, M. Mayersohn and S. Selliah, The rapid reduction of disulfiram in blood and plasma, J. Pharmacol. Exp. Ther., 1977, 202, 724–731.
67. J. C. Sarker, R. Nash, S. Boonrungsiman, D. Pugh and G. Hogarth, Diaryldithiocarbamates: Synthesis, oxidation to thiuram disulfides, Co(III) complexes [Co(S₂CNAr₂)₃] and use as single source precursors to CoS₂, Dalton Trans., 2022, 51, 13061–13070.
68. J. C. Sarker, F. Alam, P. McNaughter, D. Pugh, J. K. Cockcroft, D. J. Lewis and G. Hogarth, Synthesis of diaryl dithiocarbamate complexes of zinc and their uses as single source precursors for nanoscale ZnS, Inorg. Chim. Acta, 2023, 556, 121663.
69. J. C. Sarker, X. Xu, F. Alam, R. Nash, S. Boonrungsiman, D. Pugh, J. K. Cockcroft, D. J. Lewis and G. Hogarth, Copper diaryl-dithiocarbamate complexes and their application as single source precursors (SSPs) for copper sulfide nanomaterials, New J. Chem., 2023, 47, 12718–12727.
70. M. Kashif, A. G. Hogarth, Z. Khan, M. Imran and Z. Rehman, Platinum(II) dithiocarbamate complexes [Pt(S₂CNR₂)Cl(PAr₃)] as anticancer and DNA-damaging agents, Inorg. Chim. Acta, 2020, 512, 119853.
71. M. Imran, Z. Rehman, G. Hogarth, D. A. Tocher, G. Chaudhry, I. S. Butler, F. Belanger-Gariepy and T. Kondratyuk, Two new monofunctional platinum(II) dithiocarbamate complexes: phenanthriplatin-type axial protection, equatorial-axial conformational isomerism, and anticancer and DNA binding studies, Dalton Trans., 2020, 49, 15385–15396.
72. H.-U. Islam, A. Roffey, N. Hollingsworth, W. Bras, G. Sankar, N. H. De Leeuw and G. Hogarth, Understanding the role of zinc dithiocarbamate complexes as single source precursors to ZnS nanomaterials, Nanoscale Adv., 2020, 2, 798–807.
73. W.-D. Rudorf, Reactions of carbon disulfide with N-nucleophiles, J. Sulfur Chem., 2007, 28, 295–339.
74. A. A. Aly, A. B. Brown, T. M. I. Bedair and E. A. Ishak, Dithiocarbamate salts: biological activity, preparation, and utility in organic synthesis, J. Sulfur Chem., 2012, 33, 605–617.
75. Z.-Y. Wang, J. Li, N. Wang, H. Liu, W. Ding and K.-K. Wang, A Decade of Advances of CS₂/Amines in Three-Component Reactions, Synthesis, 2023, 55, 1159–1171.
76. A. Z. Halimehjani, R. Mohtasham, A. Shockravi and J. Martens, Multicomponent synthesis of dithiocarbamates starting from vinyl sulfones/sulfoxides and their use in polymerization reactions, RSC Adv., 2016, 6, 75223–75226.
77. R. Biswas, P. Thakur, G. Kaur, S. Som, M. Saha, V. Jhajhria, H. Singh, I. Ahmed, B. Banerjee and D. Chopra, et al. Interfacial Engineering of CuCo₂S₄/g-C₃N₄ Hybrid Nanorods for Efficient Oxygen Evolution Reaction, Inorg. Chem., 2021, 60, 12355–12366.
78. A. A. Pradhan, M. C. Uible, S. Agarwal, J. W. Turnley, S. Khandelwal, J. M. Peterson, D. D. Blach, R. N. Swope, L. Huang and S. C. Bart, et al. Synthesis of BaZrS₃ and BaHfS₃ Chalcogenide Perovskite Films Using Single-Phase Molecular Precursors at Moderate Temperatures, Angew. Chem., Int. Ed., 2023, 62, e202301049.
79. B. Prelesnik, K. Andjelkovic, Z. Markovic, T. Sabo and S. Trifunovic, Potassium 3-dithiocarboxy-3-aza-5-aminopentanoate dihydrate, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1997, 53, 719–720.
80. R. Biswas, P. Thakur, G. Kaur, S. Som, M. Saha, V. Jhajhria, H. Singh, I. Ahmed, B. Banerjee and D. Chopra, et al. Correction to Interfacial Engineering of CuCo₂S₄/g-C₃N₄ Hybrid Nanorods for Efficient Oxygen Evolution Reaction, Inorg. Chem., 2022, 61, 13226–13227.
81. J. D. E. T. Wilton-Ely, D. Solanki and G. Hogarth, Multifunctional dithiocarbamates as ligands towards the rational synthesis of polymetallic arrays: An example based on a piperazine-derived dithiocarbamate ligand, Eur. J. Inorg. Chem., 2005, 4027–4030.
82. J. D. E. T. Wilton-Ely, D. Solanki, E. R. Knight, K. B. Holt, A. L. Thompson and G. Hogarth, Multimetallic assemblies using piperazine-based dithiocarbamate building blocks, Inorg. Chem., 2008, 47, 9642–9653.
83. E. R. Knight, N. H. Leung, A. L. Thompson, G. Hogarth and J. D. E. T. Wilton-Ely, Multimetallic Arrays: Bi-, Tri-, Tetra-, and Hexametallic Complexes Based on Gold(I) and Gold(III) and the Surface Functionalization of Gold Nanoparticles with Transition Metals, Inorg. Chem., 2009, 48, 3866–3874.
84. E. R. Knight, N. H. Leung, Y. H. Lin, A. R. Cowley, D. J. Watkin, A. L. Thompson, G. Hogarth and J. D. E. T. Wilton-Ely, Multimetallic arrays: symmetrical bi-, tri- and tetrametallic complexes based on the group 10 metals and the functionalization of gold nanoparticles with nickel-phosphine surface units, Dalton Trans., 2009, 3688–3697.
85. K. Oliver, A. J. P. White, G. Hogarth and J. D. E. T. Wilton-Ely, Multimetallic complexes of group 10 and 11 metals based on polydentate dithiocarbamate ligands, Dalton Trans., 2011, 40, 5852–5864.
86. M. J. Macgregor, G. Hogarth, A. L. Thompson and J. D. E. T. Wilton-Ely, Multimetallic Arrays: Symmetrical and Unsymmetrical Bi-, Tri-, and Tetrametallic Organometallic Complexes of Ruthenium(II) and Osmium(II), Organometallics, 2009, 28, 197–208.
87. E. Humeres, N. A. Debacher, J. D. Franco, B. S. Lee and A. Martendal, Mechanisms of Acid Decomposition of Dithiocarbamates. 3. Aryldithiocarbamates and the Torsional Effect, J. Org. Chem., 2002, 67, 3662–3667.
88. S. C. Ball, I. Cragg-Hine, M. G. Davidson, R. P. Davies, A. J. Edwards, I. Lopez-Solera, P. R. Raithby and R. Snaith, Lithium intermediates during the α-lithiation and subsequent α-substitution of heterocyclic amines in the presence of CO₂, Angew. Chem., Int. Ed. Engl., 1995, 34, 921–923.
89. P. Padungros and A. Wei, Practical Synthesis of Aromatic Dithiocarbamates, Synth. Commun., 2014, 44, 2336–2343.
90. M. Uchiyama, K. Satoh and M. Kamigaito, Cationic RAFT Polymerization Using ppm Concentrations of Organic Acid, Angew. Chem., Int. Ed., 2015, 54, 1924–1928.
91. H. Ma, G. Wang, G. T. Yee, J. L. Petersen and M. P. Jensen, Scorpionate-supported models of nickel-dependent superoxide dismutase, Inorg. Chim. Acta, 2009, 362, 4563–4569.
92. B. Ballard, D. Wycoff, E. R. Birnbaum, K. D. John, J. W. Lenz, S. S. Jurisson, C. S. Cutler, F. M. Nortier, W. A. Taylor and M. E. Fassbender, Selenium-72 formation via ^natBr(p,x) induced by 100 MeV Protons: Steps towards a novel ⁷²Se/⁷²As generator system, Appl. Radiat. Isot., 2012, 70, 595–601.
93. K. S. Siddiqi and N. Nishat, Synthesis and characterization of succinimide and phthalimide dithiocarbamates and their complexes with some transition metal ions, Synth. React. Inorg. Met.-Org. Chem., 2000, 30, 1505–1518.
94. I. F. Alshdoukhi, A. S. M. O. Al-Barwari, N. M. Aziz, T. Khalil, A. S. Faihan, S. A. Al-Jibori and A. S. Al-Janabi, Pd(II), Pt(II), Zn(II), Cd(II) and Hg(II) complexes of the newly prepared 1,2-benzoisothiazol-3(2H)-dithiocarbamate (BIT-DTC) ligand, Bull. Chem. Soc. Ethiop., 2024, 38, 889–899.
95. M. Y. Mohammed, Z. M. Mustafa and F. N. Aziz, Synthesis, Characterization, and Antibacterial Activity of Co(II), Ni(II), and Pd(II) Complexes with Bisdithiocarbamate and Cyclic Amines Ligands, Macromol. Symp., 2022, 401, 2100341.
96. M. Y. Mohammed, M. G. Abdel Karim and H. M. Abdul Karim, Synthesis, Characterization, and Bacterial Activity of Co(II), Ni(II), and Pd(II) Complexes with Ligands of Thymine, Uracil Thiuram Disulfur, and Cyclic Amines, Macromol. Symp., 2022, 401, 2100310.
97. H. W. Omar, M. Y. Mohammed and A. I. Yaseen, Synthesis and Characterization of Silver(I) Macromolecules Containing Macrocyclic Dithiocarbamate Ligand and Phosphines, Macromol. Symp., 2025, 414, 2400217.
98. T. Takeshima, M. Ikeda, M. Yokoyama, N. Fukada and M. Muraoka, Reaction of carbon disulfide with cyclic amides and related compounds. Free N-acyl- and N-carbamoyl-dithiocarbamic acids, J. Chem. Soc., Perkin Trans. 1, 1979, 692–695.
99. J. Chiefari, R. T. A. Mayadunne, C. L. Moad, G. Moad, E. Rizzardo, A. Postma, M. A. Skidmore and S. H. Thang, Thiocarbonylthio Compounds (S:C(Z)S-R) in Free Radical Polymerization with Reversible Addition-Fragmentation Chain Transfer (RAFT Polymerization). Effect of the Activating Group Z, Macromolecules, 2003, 36, 2273–2283.
100. H. Aoshima, M. Uchiyama, K. Satoh and M. Kamigaito, Interconvertible Living Radical and Cationic Polymerization through Reversible Activation of Dormant Species with Dual Activity, Angew. Chem., Int. Ed., 2014, 53, 10932–10936.
101. R. Gerner, G. Kiel and G. Gattow, Chalcogenolates. 148. Reaction of formamide with carbon disulfide. 2. Crystal structure of potassium N-formyldithiocarbamate, Z. Anorg. Allg. Chem., 1985, 523, 76–88.
102. C. C. Hadjikostas and G. A. Katsoulos, Synthesis and characterization of 2-pyrrolidone-N-carbodithioato complexes of several transition metals, Int. J. Chem., 1994, 5, 49–57.
103. P. J. Heard, Y. S. Tan, C. I. Yeo and E. R. T. Tiekink, The Coordination Chemistry of Imidomethanedithiolate Di-anions: A Structural Comparison with Their Dithiocarbamate Analogs, Inorganics, 2021, 9, 71.
104. C. C. Hadjikostas, G. A. Katsoulos, M. P. Sigalas and C. A. Tsipis, Carbodithioato derivatives of weak nitrogenous nucleophiles. II. Nondirect syntheses and structural studies of nickel(II) N-carbodithioates with substituted ureas, carbamic esters and sulfonamides, Inorg. Chim. Acta, 1989, 163, 173–176.
105. C. C. Hadjikostas, G. A. Katsoulos, M. P. Sigalas and C. A. Tsipis, Carbodithioato derivatives of weak nitrogenous nucleophiles. I. Electronic structure and ground state properties of nickel(II) amide N-carbodithioates, Can. J. Chem., 1989, 67, 902–909.
106. C. C. Hadjikostas, G. A. Katsoulos, M. P. Sigalas, C. A. Tsipis and N. V. Duffy, Convenient, straightforward routes to carbodithioato derivatives of weak nitrogenous nucleophiles, Polyhedron, 1989, 8, 2637–2639.
107. J. Salah, H. P. Bridges, D. Pugh and G. Hogarth, unpublished results.
108. B. Cvek, The Promiscuity of Disulfiram in Medicinal Research, ACS Med. Chem. Lett., 2023, 14, 1610–1614.
109. A. Bera, B. Busupalli and B. L. V. Prasad, Solvent-Less Solid State Synthesis of Dispersible Metal and Semiconducting Metal Sulfide Nanocrystals, ACS Sustainable Chem. Eng., 2018, 6, 12006–12016.
110. A. Bera, D. Mandal, P. N. Goswami, A. K. Rath and B. L. V. Prasad, Generic and Scalable Method for the Preparation of Monodispersed Metal Sulfide Nanocrystals with Tuneable Optical Properties, Langmuir, 2018, 34, 13459–13460.
111. A. Bera, B. Busupalli and B. L. V. Prasad, Solvent-Less Solid State Synthesis of Dispersible Metal and Semiconducting Metal Sulfide Nanocrystals, ACS Sustainable Chem. Eng., 2018, 6, 12006–12016.
112. C. Jin, Y. Li, J. Lin, X. Guo, Y. Shi, H. Zhu, Y. Wang and X. Zhang, Efficient Transition Metal Sulfide Electrocatalysts Prepared by Laser-Induced Precursor Decomposition, Appl. Energy Mater., 2024, 7, 8546–8533.
113. S. J. Joris, K. I. Aspila and C. L. Chakrabarti, Monobasic or dibasic character of dithiocarbamic acids, Anal. Chem., 1969, 41, 1441–1445.
114. S. J. Joris, K. I. Aspila and C. L. Chakrabarti, On the Mechanism of Decomposition of Dithiocarbamates, J. Phys. Chem., 1970, 74, 860–865.
115. R. R. Vandebeek, S. J. Joris, K. I. Aspila and C. L. Chakrabarti, Decomposition of some cyclic dithiocarbamates, Can. J. Chem., 1970, 48, 2204–2209.
116. K. I. Aspila, S. J. Joris and C. L. Chakrabarti, Solvent Isotope Effects on Decomposition of N,N′-Dialkyldithiocarbamic Acids, Anal. Chem., 1971, 43, 1529–1530.
117. D. De Filippo, P. Deplano, F. Devillanova, E. F. Trogu and G. Verani, Inductive effect in dithiocarbamate decomposition mechanism, J. Org. Chem., 1973, 38, 560–563.
118. F. Takami, K. Tokuyama, S. Wakahara and T. Maeda, Decomposition of dithiocarbamates. VI. Decomposition of N-monosubstituted dithiocarbamic acids in acidic solutions, Chem. Pharm. Bull., 1973, 21, 594–599.
119. E. Humeres, N. A. Debacher, M. de Marta, J. D. Franco and A. Schutz, Mechanisms of Acid Decomposition of Dithiocarbamates. 1. Alkyl Dithiocarbamates, J. Org. Chem., 1998, 63, 1598–1603.
120. E. Humeres, N. A. Debacher and M. M. D. S. Sierra, Mechanisms of Acid Decomposition of Dithiocarbamates. 2. Efficiency of the Intramolecular General Acid Catalysis, J. Org. Chem., 1999, 64, 1807–1813.
121. E. Humeres, N. A. Debacher, J. D. Franco, B. S. Lee and A. Martendal, Mechanisms of Acid Decomposition of Dithiocarbamates. 3. Aryldithiocarbamates and the Torsional Effect, J. Org. Chem., 2002, 67, 3662–3667.
122. E. Humeres, B. S. Lee and N. A. Debacher, Mechanisms of Acid Decomposition of Dithiocarbamates. 5. Piperidyl Dithiocarbamate and Analogues, J. Org. Chem., 2008, 73, 7189–7196.
123. M. L. Riekkola and H. Siren, The rate of decomposition of sodium diisobutyldithiocarbamate in aqueous solution and extractability of the corresponding acid with methylene chloride, Finn. Chem. Lett., 1983, 68–73.
124. V. Amarnath, K. Amarnath and W. M. Valentine, Mechanism of decomposition of N,N-dialkyl dithiocarbamates, Curr. Top. Toxicol., 2007, 4, 39–44.
125. A. W. DeMartino, M. L. Souza and P. C. Ford, Uncaging carbon disulfide. Delivery platforms for potential pharmacological applications: a mechanistic approach, Chem. Sci., 2017, 8, 7186–7196.
126. Y. Gao and B. Xia, Microdroplet accelerated reaction for high-efficiency carbon disulfide conversion, Chem. Commun., 2023, 59, 10773–10776.
127. B. Maeda and K. Murakami, Recent advancement in the synthesis of isothiocyanates, Chem. Commun., 2024, 60, 2839–2864.
128. R. Wong and S. J. Dolman, Isothiocyanates from Tosyl Chloride Mediated Decomposition of in Situ Generated Dithiocarbamic Acid Salts, J. Org. Chem., 2007, 72, 3969–3971.
129. S. Murru, H. Ghosh, S. K. Sahoo and B. K. Patel, Intra- and Intermolecular C-S Bond Formation Using a Single Catalytic System: First Direct Access to Arylthiobenzothiazoles, Org. Lett., 2009, 11, 4254–4257.
130. B. Luo, Q. Cui, H. Luo, Y. Hu, P. Huang and S. Wen, N-Benzyldithiocarbamate Salts as Sulfur Sources to Access Tricyclic Thioheterocycles Mediated by Copper Species, Adv. Synth. Catal., 2016, 358, 2733–2738.
131. A. Z. Halimehjani, S. Shokrgozar and P. Beier, Transition-Metal-Free Coupling Reaction of Dithiocarbamates with Indoles: C-S Bond Formation, J. Org. Chem., 2018, 83, 5778–5783.
132. J. Nath, H. Ghosh, R. Yella and B. K. Patel, Molecular Iodine Mediated Preparation of Isothiocyanates from Dithiocarbamic Acid Salts, Eur. J. Org. Chem., 2009, 1849–1851.
133. J. Nath, P. Jamir and B. K. Patel, Improved procedure for the preparation of isothiocyanates via iodine-mediated desulfurization of dithiocarbamic acid salts, Green Chem. Lett. Rev., 2011, 4, 1–34.
134. H. C. Brinkhoff, J. A. Cras, J. J. Steggerda and J. Willemse, Oxidation of dithiocarbamate complexes of nickel, copper, and zinc, Recl. Trav. Chim. Pays-Bas, 1969, 88, 633–640.
135. S. Thirumaran, K. Ramalingam, G. Bocelli and A. Cantoni, Spectral and single crystal X-ray structural studies on disulfide complexes: reaction of bis(dialkyldithiocarbamato)M(II) with iodine and crystal structure determination of diiodo(bipiperidinethiuramdisulfide)M(II) (M = zinc, cadmium), Polyhedron, 2000, 19, 1279–1282.
136. F. Liang, J. Tan, C. Piao and Q. Liu, Carbon tetrabromide promoted reaction of amines with carbon disulfide: facile and efficient synthesis of thioureas and thiuram disulfides, Synthesis, 2008, 3579–3584.
137. S. Techapanalai, R. M. Annuur, M. Sukwattanasinitt and S. Wach, arasindhu, One-Pot Synthesis of Isothiocyanates from Amines Mediated by Carbon Tetrabromide, ChemistrySelect, 2023, 8, e202302045.
138. Z. Fu, W. Yuan, N. Chen, Z. Yang and J. Xu, Na₂S₂O₈-mediated efficient synthesis of isothiocyanates from primary amines in water, Green Chem., 2018, 20, 4484–4491.
139. D. Li, Y. Shu, P. Li, W. Zhang, H. Ni and Y. Cao, Synthesis and structure-activity relationships of aliphatic isothiocyanate analogs as antibiotic agents, Med. Chem. Res., 2013, 22, 3119–3125.
140. J. Ma, F. Li, C. Wang, Z. Wang, C. Du and L. Wang, Synthesis of Isothiocyanates from Primary Amines via Visible-Light Photocatalysis, Org. Lett., 2023, 25, 5692–5696.
141. There were 3749 hits in the CSD version 5.45 (November 2023) for metal dithiocarbamate complexes.
142. D. V. Konarev, A. Y. Kovalevsky, S. S. Khasanov, G. Saito, D. V. Lopatin, A. V. Umrikhin, A. Otsuka and R. N. Lyubovskaya, Synthesis, crystal structures, magnetic properties and photoconductivity of C₆₀ and C₇₀ complexes with metal dialkyldithiocarbamates M(R₂dtc)_x, where M = CuII, CuI, AgI, ZnII, CdII, HgII, MnII, NiII, and PtII; R = Me, Et, and nPr, Eur. J. Inorg. Chem., 2006, 1881–1895.
143. D. V. Konarev, S. S. Khasanov, D. V. Lopatin, V. V. Rodaev and R. N. Lyubovskaya, Fullerene complexes with divalent metal dithiocarbamates: structures, magnetic properties, and photoconductivity, Russ. Chem. Bull., 2007, 56, 2145–2161.
144. D. V. Konarev, S. S. Khasanov, A. Y. Kovalevsky, D. V. Lopatin, V. V. Rodaev, G. Saito, B. Nara, L. Forro and R. N. Lyubovskaya, Supramolecular approach to the synthesis of [60]fullerene-metal dithiocarbamate complexes, {(MII(R₂dtc)₂)_x·L}·C₆₀ (M = Zn, Cd, Hg, Fe, and Mn; x = 1 and 2). The study of magnetic properties and photoconductivity, Cryst. Growth Des., 2008, 8, 1161–1172.
145. E. C. Alyea, D. C. Bradley, M. F. Lappert and A. R. Sanger, Lower valent dialkylamides of titanium and vanadium, J. Chem. Soc., Chem. Commun., 1969, 1064–1065.
146. D. C. Bradley and M. H. Gitlitz, Preparation and Properties of N,N-Dialkyldithiocarbamates of Early Transition Elements, J. Chem. Soc. A, 1969, 1152–1156.
147. A. C. Behrle, A. J. Myers, A. Kerridge and J. R. Walensky, Coordination Chemistry and QTAIM Analysis of Homoleptic Dithiocarbamate Complexes, M(S₂CNⁱPr₂)₄ (M = Ti, Zr, Hf, Th, U, Np), Inorg. Chem., 2018, 57, 10518–10524.
148. M. Colapietro, A. Vaciago, D. C. Bradley, M. B. Hursthouse and I. F. Rendall, Structural studies of metal dithiocarbamates. VI. Crystal and molecular structure of tetrakis(N,N-diethyldithiocarbamato)titanium(IV), J. Chem. Soc., Dalton Trans., 1972, 1052–1057.
149. G. L. Campbell, G. D. Ellis and M. R. Chakrabarty, The synthesis and characterization of some titanium(III) tris-N,N-dialkyldithiocarbamates, J. Inorg. Nucl. Chem., 1981, 43, 2265–2268.
150. R. E. Jilek, G. Tripepi, E. Urnezius, W. W. Brennessel, V. G. Young Jr. and J. E. Ellis, Zerovalent titanium-sulfur complexes. Novel dithiocarbamato derivatives of Ti(CO)₆: [Ti(CO)₄(S₂CNR₂)]⁻, Chem. Commun., 2007, 2639–2641.
151. L. F. Larkworthy and M. W. O'Donoghue, Synthesis and properties of vanadium(III) dithiocarbamates, Inorg. Chim. Acta, 1983, 74, 155–158.
152. H. P. Zhu, Y.-H. Deng, X.-Y. Huang, C.-N. Chen and Q.-T. Liu, Tris(N,N-diethyldithiocarbamato-S,S’)vanadium(III), Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1997, 53, 692–693.
153. S. Sproules, T. Weyhermueller, S. De Beer and K. Wieghardt, Six-Membered Electron Transfer Series [V(dithiolene)₃]z (z = 1+, 0, 1-, 2-, 3-, 4-). An X-ray Absorption Spectroscopic and Density Functional Theoretical Study, Inorg. Chem., 2010, 49, 5241–5261.
154. T. L. Riechel, L. J. De Hayes and D. T. Sawyer, Electrochemical studies of vanadium(III), -(IV), and -(V) complexes of diethyldithiocarbamate in acetonitrile, Inorg. Chem., 1976, 15, 1900–1904.
155. D. C. Bradley, I. F. Rendall and K. D. Sales, Covalent compounds of quadrivalent transition metals. VI. Spectroscopic studies on titanium, vanadium, and zirconium diethyldithiocarbamates, J. Chem. Soc., Dalton Trans., 1973, 2228–2233.
156. B. J. McCormick, Structure and spectra of dithiocarbamate complexes of oxovanadium(IV), Inorg. Chem., 1968, 7, 1965–1970.
157. H. Sakurai, H. Watanabe, H. Tamura, H. Yasui, R. Matsushita and J. Takada, Insulin-mimetic vanadyl-dithiocarbamate complexes, Inorg. Chim. Acta, 1998, 283, 175–183.
158. M. Atzori, L. Tesi, S. Benci, A. Lunghi, R. Righini, A. Taschin, R. Torre, L. Sorace and R. Sessoli, Spin Dynamics and Low Energy Vibrations: Insights from Vanadyl-Based Potential Molecular Qubits, J. Am. Chem. Soc., 2017, 139, 4338–4341.
159. R. M. Golding, P. C. Healy, P. Colombera and A. H. White, NMR studies of some chromium(III) dithicarbamate complexes, Aust. J. Chem., 1974, 27, 2089–2097.
160. C. L. Raston and A. H. White, Crystal structure of tris(N,N-diethyldithiocarbamato) chromium(III), Aust. J. Chem., 1977, 30, 2091–2094.
161. D. J. Lewis, A. A. Tedstone, X. L. Zhong, E. A. Lewis, A. Rooney, N. Savjani, J. R. Brent, S. J. Haigh, M. G. Burke and C. A. Muryn, et al., Thin Films of Molybdenum Disulfide Doped with Chromium by Aerosol-Assisted Chemical Vapor Deposition (AACVD), Chem. Mater., 2015, 27, 1367–1374.
162. J. P. Fackler Jr. and D. G. Holah, Sulfur chelates. II. Five-coordinate transition metal complexes, Inorg. Nucl. Chem. Lett., 1966, 2, 251–255.
163. R. Lancashire and T. D. Smith, Syntheses of diethyldithiocarbamate chelates of chromium(III) and molybdenum(V) by oxidative decarbonylation, J. Chem. Soc., Dalton Trans., 1982, 845–846.
164. A. M. Bond and G. G. Wallace, Influence of oxygen insertion on the electrochemistry of chromium(III) dithiocarbamate complexes, Inorg. Chem., 1984, 23, 1858–1865.
165. L. Y. Goh, Z. Weng, W. K. Leong and P. H. Leung, C-S bond cleavage and C-C coupling in cyclopentadienylchromium complexes to give the first dithiooxamide-bridged and doubly dithiocarbamate-bridged double cubanes: [Cp₆Cr₈S₈{(C(S)NEt₂)₂}] and [Cp₆Cr₈S₈(S₂CNEt₂)₂], Angew. Chem., Int. Ed., 2001, 40, 3236–3239.
166. G.-Y. He, F.-L. Bei, H.-Q. Chen and X.-Q. Sun, Solid-phase synthesis, crystal structure, and quantum chemical calculation of a molybdenum(II) complex with bis(diethyldithiocarbamate), J. Chem. Crystallogr., 2006, 36, 481–486.
167. R. Selvaraju, K. Panchanatheswaren, A. Thiruvalluvar and V. Parthasarathi, Redetermination of Bis(N,N-diethyldithiocarbamato)nickel(II), Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1995, 51, 606–608.
168. P. Vella and J. Zubieta, Preparation, characterization and electrochemical investigation of dimeric molybdenum thioxanthate complexes, Mo₂(S₂CSR)₄, and their relationship to analogous binuclear dithioacid complexes, J. Inorg. Nucl. Chem., 1978, 40, 477–487.
169. L. Ricard, J. Estienne and R. Weiss, Formation of a thiocarboxamidomolybdenum complex by oxidative bond cleavage. Crystal and molecular structure of bis[μ-sulfido-thiocarboxamido(dipropyldithiocarbamato)molybdenum], Inorg. Chem., 1973, 12, 2182–2186.
170. J. A. Broomhead and C. G. Young, Tungsten carbonyl complexes with dithiocarbamate ligands, Aust. J. Chem., 1982, 35, 277–285.
171. S. J. N. Burgmayer and J. L. Templeton, Synthesis and structure of a seven-coordinate molybdenum carbonyl fluoride derivative: [Et₄N][Mo(CO)₂(S₂CNEt₂)₂F], Inorg. Chem., 1985, 24, 2224–2230.
172. D. M. Hill, L. F. Larkworthy and M. W. O'Donoghue, Manganese(II) compounds of N,N-disubstituted dithiocarbamates, J. Chem. Soc., Dalton Trans., 1975, 1726–1728.
173. G. Reale, F. Calderoni, T. Ghirardi, F. Porto, F. Illuminati, L. Marvelli, P. Martini, L. Uccelli, E. Tonini, L. Del Bianco, F. Spizzo, M. Capozza, E. Cazzola, A. Carnevale, M. Giganti, A. Turra, J. Esposito and A. Boschi, Development and Evaluation of the Magnetic Properties of a New Manganese(II) Complex: A Potential MRI Contrast Agent, Int. J. Mol. Sci., 2023, 24, 3461.
174. M. Ciampolini, C. Mengozzi and P. Orioli, Structure and magnetic properties of bis(diethyldithiocarbamato)manganese(II), J. Chem. Soc., Dalton Trans., 1975, 2051–2054.
175. P. Martini, A. Boschi, L. Marvelli, L. Uccelli, S. Carli, G. Cruciani, E. Marzola, A. Fantinati, J. Esposito and A. Duatti, Synthesis and Characterization of Manganese Dithiocarbamate Complexes: New Evidence of Dioxygen Activation, Molecules, 2021, 26, 5954.
176. J. Qu, A. Elgendy, R. Cai, M. A. Buckingham, A. A. Papaderakis, H. de Latour, K. Hazeldine, G. F. S. Whitehead, F. Alam, C. T. Smith, D. J. Binks, A. Walton, J. M. Skelton, R. A. W. Dryfe, S. J. Haigh and D. J. Lewis, A Low-Temperature Synthetic Route Toward a High-Entropy 2D Hexernary Transition Metal Dichalcogenide for Hydrogen Evolution Electrocatalysis, Adv. Sci., 2023, 10, 2204488.
177. Y.-W. Jun, Y.-Y. Jung and J. Cheon, Architectural Control of Magnetic Semiconductor Nanocrystals, J. Am. Chem. Soc., 2002, 124, 615–619.
178. Y. Yang, O. Chen, A. Angerhofer and C. Y. Cao, Radial-Position-Controlled Doping in CdS/ZnS Core/Shell Nanocrystals, J. Am. Chem. Soc., 2006, 128, 12428–12429.
179. Y. Zhang, R. Xu, W. Chen, O. Zhuo, Q. Wu, J. Cai, X. Wang and Z. Hu, Solution-solid-solid growth of metastable wurtzite γ-MnS nanowires with controlled length, J. Mater. Chem. C, 2017, 5, 6493–6496.
180. Y. Zhang, Y. Xue, K. Qi, Z. Ru, J. Cai and W. Chen, Construction of Various One-Dimensional ZnS/MnS Hetero-nanostructures with Varied Diameters via the Multistep Solution-Solid-Solid Growth Method, Inorg. Chem., 2022, 61, 1152–1158.
181. H. B. Ferraz, P. H. Bertolucci, J. S. Pereira, J. G. Lima and L. A. Andrade, Chronic exposure to the fungicide maneb may produce symptoms and signs of CNS manganese intoxication, Neurology, 1988, 38, 550–553.
182. S. Costello, M. Cockburn, J. Bronstein, X. Zhang and B. Ritz, Parkinson's disease and residential exposure to maneb and paraquat from agricultural applications in the central valley of California, Am. J. Epidemiol., 2009, 169, 919–926.
183. L. Kubens, K.-N. Truong, C. W. Lehmann, D. Luetzenkirchen-Hecht, J. Bornhorst and F. Mohr, The Structure of Maneb, An Important Manganese-Containing Bis(dithiocarbamate) Fungicide, Chem. – Eur. J., 2023, 29, e202301721.
184. J. G. Lozano, F. Dillon, A. J. Naylor, L. Y. Lee, C. Lippard, D. Johnstone, P. G. Bruce and N. Grobert, Single Source Precursor Route to Iron Sulfide Nanomaterials for Energy Storage, Chem. Phys. Lett., 2020, 739, 136993.
185. O. A. Ileperuma and R. D. Feltham, Crystal and molecular structure of iron(II) bis(diethyldithiocarbamate), Inorg. Chem., 1975, 14, 3042–3045.
186. J. Lu, C.-H. Lu, J.-H. Yu, J.-Q. Xu, Y. Li, X. Zhang, T.-G. Wang and Q.-X. Yang, Syntheses, structures and third-order nonlinear optical properties of heterometal and homometal clusters containing iron, Polyhedron, 2004, 23, 755–761.
187. L. F. Larkworthy, B. W. Fitzsimmons and R. R. Patel, Magnetic and Mossbauer investigation of N,N-disubstituted(dithiocarbamato)-iron(II) complexes, J. Chem. Soc., Chem. Commun., 1973, 902–903.
188. B. W. Fitzsimmons, S. E. Al-Mukhtar, L. F. Larkworthy and R. R. Patel, Magnetic and Mössbauer investigations of N,N-disubstituted bis(dithiocarbamato)iron(II) complexes, J. Chem. Soc., Dalton Trans., 1975, 1969–1973.
189. R. H. Holm, L. H. Pinolet and R. A. Lewis, Synthesis and stereochemical rearrangements of complexes containing the Fe-S6 core, J. Am. Chem. Soc., 1971, 93, 360–371.
190. J. L. K. F. De Vries, J. M. Trooster and E. De Boer, Iron(II) complexes with two and three dialkyldithiocarbamate ligands. Mössbauer and electronic spectra, Inorg. Chem., 1973, 12, 2730–2733.
191. Y. Deng, T. Wen, Q. Liu, H. Zhu, C. Chen and D. Wu, Structure and characterization of a mononuclear FeII dialkyldithiocarbamate complex Fe(OC₄H₈dtc)₂(DMF), Inorg. Chim. Acta, 1999, 293, 95–99.
192. M. R. Houchin, Reactions of carbon monoxide with iron(II) diethyldithiocarbamate and iron(II) ethylxanthate, Inorg. Chim. Acta, 1984, 83, 103–110.
193. G. Hogarth, N. Hollingsworth, H. Islam, W. Bras, N. H. De Leeuw, A. Roffey and G. Sankar, Fe(II) and Fe(III) dithiocarbamate complexes as single source precursors to nanoscale iron sulfides: A combined synthetic and in situ XAS approach, Nanoscale Adv., 2019, 1, 2965–2978.
194. G. R. Davies, J. A. J. Jarvis, B. T. Kilbourn, R. H. B. Mais and P. G. Owston, Crystal and molecular structure of bis-(N,N-dimethyldithiocarbamato)-nitrosyliron (at −80 deg.), J. Chem. Soc. A, 1970, 1275–1283.
195. O. A. Ileperuma and R. D. Feltham, Iron-sulfur complexes of nitric oxide. 2. Synthesis and exchange studies of Fe(NO)X[S₂CN(CH₃)₂]₂. Crystal and molecular structure of cis-bis(diethyldithiocarbamato)(nitro)nitrosyliron, Inorg. Chem., 1977, 16, 1876–1883.
196. P. Mordvintcev, A. Muelsch, R. Busse and A. Vanin, On-line detection of nitric oxide formation in liquid aqueous phase by electron paramagnetic resonance spectroscopy, Anal. Biochem., 1991, 199, 142–146.
197. C. Csonka, T. Pali, P. Bencsik, A. Goerbe, P. Ferdinandy and T. Csont, Measurement of NO in biological samples, Br. J. Pharmacol., 2015, 172, 1620–1632.
198. S. Fujii and T. Yoshimura, A new trend in iron-dithiocarbamate complexes: as an endogenous NO trapping agent, Coord. Chem. Rev., 2000, 198, 89–99.
199. H. Kunkely and A. Vogler, Photochemistry of tris(diethyldithiocarbamato)iron(III). Reduction to a stable iron(II) complex induced by ligand-to-metal charge transfer excitation, Inorg. Chem. Commun., 2002, 5, 730–732.
200. W.-H. Leung, J. L. C. Chim, H. Hou, T. S. M. Hun, I. D. Williams and W.-T. Wong, Oxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II), Inorg. Chem., 1997, 36, 4432–4437.
201. M. Md. Karim, N. Md. Abser, M. R. Hassan, N. Ghosh, H. G. Alt, I. Richards and G. Hogarth, Oxidative-addition of thiuram disulfides to osmium(0): Synthesis of cis-[Os(CO)₂(S₂CNR₂)₂] (R = Me, Et, Cy, CH₂CH₂OMe) and molecular structures of cis-[Os(CO)₂(S₂CNMe₂)₂] and [(MeOCH₂CH₂)₂NCS]₂, Polyhedron, 2012, 42, 84–88.
202. Md. N. Huda, J. C. Sarker, V. N. Nesterov, G. Hogarth and S. E. Kabir, Oxidative-addition of tetramethylthiram disulfide (Me₄TDS) and monosulfide (Me₄TMS) at a triosmium centre: Generation of dithiocarbamate, trithiocarbamate, thiocarboxamide and amino-carbyne ligands, J. Organomet. Chem., 2024, 1016, 123252.
203. N. C. Bhoumik, Md. N. Huda, V. N. Nesterov, G. Hogarth, S. E. Kabir and J. C. Sarker, Reactivity of Labile Triosmium Complexes, [Os₃(CO)₁₀(MeCN)₂] and [Os₃(CO)₁₀(μ-H)₂] with Tetraethylthiuram Disulfide (Disulfiram), J. Cluster Sci., 2025, 36, 34.
204. R. M. Golding, P. C. Healy, P. W. G. Newman, E. Sinn and A. H. White, Temperature dependence of the proton nuclear magnetic resonance spectra of some diamagnetic N,N-dialkyldithiocarbamate complexes of transition metals, Inorg. Chem., 1972, 11, 2435–2440.
205. P. C. Healy, J. W. Connor, B. W. Skelton and A. H. White, Alkyl substituent effects in diamagnetic dithiocarbamate cobalt(III) and nickel(II) complexes, Aust. J. Chem., 1990, 43, 1083–1095.
206. F. Jian, F. Bei, P. Zhao, X. Wang, H. Fun and K. Chinnakali, Synthesis, crystal structure and stability studies of dithiocarbamate complexes of some transition elements (M = Co, Ni, Pd), J. Coord. Chem., 2002, 55, 429–437.
207. N. V. Khitrich, V. G. Vlasenko, I. I. Seifullina, Ya. V. Zubavichus, S. I. Levchenkov and L. S. Skorokhod, Local surrounding of cobalt(II) in dithiocarbamate complexes, their magnetic and spectral properties, Russ. J. Gen. Chem., 2014, 84, 555–561.
208. A. M. Bond, A. R. Hendrickson, R. L. Martin, J. E. Moir and D. R. Page, Electrochemical reduction and oxidation of cobalt(III) dithiocarbamates, Inorg. Chem., 1983, 22, 3440–3446.
209. G. Hogarth, K. T. Holman, A. Pateman, A. Sella, J. W. Steed and I. Richards, Multiple nitrene insertions into metal-sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes, Dalton Trans., 2005, 2688–2695.
210. K. K. Pandey, D. T. Nehete and R. B. Sharma, Square planar and square pyramidal complexes of rhodium(II), Polyhedron, 1990, 9, 2013–2018.
211. N. M. Sosibo and N. Revaprasadu, Synthesis and characterization of rhodium sulfide nanoparticles and thin films, Mater. Sci. Eng., B, 2008, 150, 111–115.
212. C. L. Raston and A. H. White, Crystal structures of tris(diethyldithiocarbamato)rhodium(III) and -arsenic(III), J. Chem. Soc., Dalton Trans., 1975, 2425–2429.
213. C. G. Sceney and R. J. Magee, Iridium(III) dithiocarbamate complexes, Inorg. Nucl. Chem. Lett., 1973, 9, 595–597.
214. A. M. Bond, R. Colton and D. R. Mann, Electrochemical investigation of kinetic and thermodynamic aspects of oxidation and reduction of mononuclear and binuclear rhodium dithiocarbamate and diselenocarbamate complexes, Inorg. Chem., 1989, 28, 54–59.
215. S. Lahiry and V. K. Anand, Manganese(II) complex in a pure spin quartet state, J. Chem. Soc., Chem. Commun., 1971, 1111–1112.
216. S. Tellez, C. A. Costa Jr., M. A. Mondragon, G. B. Ferreira, O. Versiane, J. L. Rangel, G. Lima and M. A. A. Muller, Molecular structure, natural bond analysis, vibrational and electronic spectra, surface enhanced Raman scattering and Mulliken atomic charges of the normal modes of [Mn(DDTC)₂] complex, Spectrochim. Acta, Part A, 2016, 169, 95–107.
217. C. A. T. Zepeda, A. Coelho, O. Versiane, M. A. Mondragon, R. S. Pessoa and C. A. Téllez Soto, Synthesis, structure determination, NBO analysis and vibrational/electronic spectroscopic study of Iron(II) Bis(diethyldithiocarbamate) [Fe(DDTC)₂], J. Mol. Struct., 2023, 1287, 135618.
218. A. C. Costa Jr., O. Versiane, O. G. Faget, J. M. Ramos, G. B. Ferreira, A. A. Martin and C. A. Téllez Soto, An experimental and theoretical approach of spectroscopic and structural properties of the bis(diethyldithiocarbamate)-cobalt(II), J. Mol. Struct., 2012, 1029, 119–134.
219. R. R. Eley, R. R. Myers and N. V. Duffy, Electron spin crossover in iron(III) dithiocarbamates, Inorg. Chem., 1972, 11, 1128–1130.
220. H. L. Nigam, K. B. Pandeya and R. Singh, ⁶A_1g⇌²T_2g spin-crossover in iron(III) dithiocarbamates, J. Indian Chem. Soc., 2001, 78, 525–532.
221. A. H. Ewald, R. L. Martin, E. Sinn and A. H. White, Electronic equilibrium between the 6A¹ and 2T² states in iron(III) dithio chelates, Inorg. Chem., 1969, 8, 1837–1846.
222. C. Milsmann, S. Sproules, E. Bill, T. Weyhermueller, S. D. George and K. Wieghardt, Stabilization of High-Valent FeIVS₆-Cores by Dithiocarbamate(1-) and 1,2-Dithiolate(2-) Ligands in Octahedral [FeIV(Et₂dtc)_3(-n(mnt)_n]⁽ⁿ⁻¹⁾⁻ Complexes (n = 0, 1, 2, 3): A Spectroscopic and Density Functional Theory Computational Study, Chem. – Eur. J., 2010, 16, 3628–3645.
223. L. H. Pignolet, Dynamic stereochemistry of tris-chelate complexes. IV. Crystal structure of tris(N,N-diethyldithiocarbamato)ruthenium(III), Inorg. Chem., 1974, 13, 2051–2055.
224. R. E. DeSimone, Electron paramagnetic resonance studies of low-spin d5 complexes. Trisbidentate complexes of iron(III), ruthenium(III), and osmium(III) with sulfur-donor ligands, J. Am. Chem. Soc., 1973, 95, 6238–6244.
225. G. R. Hall and D. N. Hendrickson, Ferric tris(dithiocarbamate) spin equilibrium revisited. Variable-temperature (4.2–296 deg K) magnetic susceptibility, (30–300 deg K) infrared, and (4.2–85 deg K) electron paramagnetic resonance data, Inorg. Chem., 1976, 15, 607–618.
226. A. M. Paca, M. Singh and P. A. Ajibade, Synthesis, characterization and in vitro anticancer studies of Ru(III) dithiocarbamate complexes, J. Coord. Chem., 2022, 75, 2923–2932.
227. J. Z. Mbese and P. A. Ajibade, Synthesis, spectroscopic, structural and optical studies of Ru₂S₃ nanoparticles prepared from single-source molecular precursors, J. Mol. Struct., 2017, 1143, 274–281.
228. J. Z. Mbese and P. A. Ajibade, Homonuclear tris-dithiocarbamato ruthenium(III) complexes as single-molecule precursors for the synthesis of ruthenium(III) sulfide nanoparticles, J. Sulfur Chem., 2017, 38, 173–187.
229. L. Giovagnini, S. Sitran, I. Castagliuolo, P. Brun, M. Corsini, P. Zanello, A. Zoleo, A. Maniero, B. Biondi and D. Fregona, Ru(III)-based compounds with sulfur donor ligands: synthesis, characterization, electrochemical behaviour and anticancer activity, Dalton Trans., 2008, 6699–6708.
230. E. M. Nagy, C. Nardon, L. Giovagnini, L. Marchio, A. Trevisan and D. Fregona, Promising anticancer mono- and dinuclear ruthenium(III) dithiocarbamato complexes: systematic solution studies, Dalton Trans., 2011, 40, 11885–11895.
231. L. Brustolin, C. Nardon, N. Pettenuzzo, N. Zuin Fantoni, S. Quarta, F. Chiara, A. Gambalunga, A. Trevisan, L. Marchio and P. Pontisso, et al., Synthesis, chemical characterization and cancer cell growth-inhibitory activities of Cu(II) and Ru(III) aliphatic and aromatic dithiocarbamato complexes, Dalton Trans., 2018, 47, 15477–15486.
232. A. R. Hendrickson, J. M. Hope and R. L. Martin, Tris- and pentakis-dialkyldithiocarbamates of ruthenium, [Ru(S₂CNR₂)₃]_n and [Ru₂(S₂CNR₂)₅]_n (n = +1, 0, and −1): chemical and electrochemical interrelations, J. Chem. Soc., Dalton Trans., 1976, 2032.
233. K. W. Given, S. H. Wheeler, B. S. Jick, L. J. Maheu and L. H. Pignolet, Synthesis, characterization, and electrochemical properties of dithiocarbamato complexes of osmium(III) and -(IV), Inorg. Chem., 1979, 18, 1261–1266.
234. E. R. T. Tiekink and I. Haiduc, Stereochemical aspects of metal xanthate complexes: Molecular structures and supramolecular self-assembly, Prog. Inorg. Chem., 2005, 54, 127–319.
235. P. J. Heard, K. Kite, J. S. Nielsen and D. A. Tocher, Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C-N bond rotation, Dalton Trans., 2000, 1349–1356.
236. M. Moriyasu, Y. Hashimoto and M. Endo, Kinetic studies of fast equilibrium by means of high-performance liquid chromatography. IV. Separation of rotamers of palladium(II) dithiocarbamates, Bull. Chem. Soc. Jpn., 1983, 56, 1972–1977.
237. W. H. Pan, T. R. Halbert, L. L. Hutchings and E. I. Stiefel, Ligand and induced internal electron transfer pathways to new molybdenum-sulfur and tungsten-sulfur dithiocarbamate complexes, J. Chem. Soc., Chem. Commun., 1985, 927–929.
238. M. A. Harmer, T. R. Halbert, W. H. Pan, C. L. Coyle, S. A. Cohen and E. I. Stiefel, Ligand and induced internal redox processes in molybdenum- and tungsten-sulfur systems, Polyhedron, 1986, 5, 341–347.
239. T. R. Halbert, L. L. Hutchings, R. Rhodes and E. I. Stiefel, Induced redox reactivity of tetrathiovanadate(V): synthesis of the vanadium(IV) dimer V₂(μ-S₂)₂(iso-Bu₂NCS₂)₄ and its structural relationship to the V/S mineral patronite, J. Am. Chem. Soc., 1986, 108, 6437–6438.
240. L. Wei, T. R. Halbert, H. H. Murray III and E. I. Stiefel, Induced internal electron transfer reactivity of tetrathioperrhenate(VII): synthesis of the interconvertible dimers Re₂(μ-S)₂(S₂CNR₂)₄ and [Re₂(μ-SS₂CNR₂)₂(S₂CNR₂)₃][O₃SCF₃] (R = Me, iso-Bu), J. Am. Chem. Soc., 1990, 112, 6431–6433.
241. Y. Gea, M. A. Greaney, C. I. Coyle and E. I. Stiefel, Analogous reactivity of MoS₄²⁻ and WSe₄²: preparation of WSe₂(iso-Bu₂NCS₂)₃ by an induced internal redox reaction, J. Chem. Soc., Chem. Commun., 1992, 160–161.
242. J. M. Hope, R. L. Martin, D. Taylor and A. H. White, Ring expansion in a metal-dithiocarbamate complex by oxygen insertion; synthesis and properties of [Cr(S₂CNR₂)₂(OS₂CNR₂)]. The X-ray structure of bis[NN-diethyl(dithiocarbamato-SS’)][NN-diethyl(dithioperoxycarbamato-OS)]chromium(III), J. Chem. Soc., Chem. Commun., 1977, 99–100.
243. S. Ng, J. W. Ziller and P. J. Farmer, Multiple Pathways for the Oxygenation of a Ruthenium(II) Dithiocarbamate Complex: S-Oxygenation and S-Extrusion, Inorg. Chem., 2004, 43, 8301–8309.
244. D. F. Brayton, K. Tanabe, M. Khiterer, K. Kolahi, J. Ziller, J. Greaves and P. J. Farmer, Oxygenation of Zinc Dialkyldithiocarbamate Complexes: Isolation, Characterization, and Reactivity of the Stoichiometric Oxygenates, Inorg. Chem., 2006, 45, 6064–6072.
245. E. Eijarvi, L. H. J. Lajunen and M. Heikka, Simultaneous determination of chromium(III) and chromium(VI) by reversed-phase high performance liquid chromatography with UV detection, Finn. Chem. Lett., 1985, 225–230.
246. Y. Honma, Formation of two chromium(III) dithiocarbamates from Cr(VI) in solvent extraction system and origin of oxygen atom in bis(1-pyrrolidinecarbodithioato)[1-pyrrolidinecarbothio (thioperoxoato)]chromium(III), Bull. Chem. Soc. Jpn., 2002, 75, 2415–2421.
247. M. Safari, S. Nojavan, S. S. H. Davarani and A. Morteza-Najarian, Speciation of chromium in environmental samples by dual electromembrane extraction system followed by high performance liquid chromatography, Anal. Chim. Acta, 2013, 789, 58–64.
248. L. F. Shvydka, Yu. I. Usatenko and F. M. Tulyupa, Strength of osmium(VI) dithiocarbamates, Zh. Neorg. Khim., 1973, 18, 756–761.
249. W. P. Griffith and J. M. Jolliffe, Studies on transition-metal nitrido and oxo complexes. Part 14. Carboxylato oxo-osmium(VI) and -ruthenium(VI) complexes and their reactions, J. Chem. Soc., Dalton Trans., 1992, 3483–3488.
250. C. Nardon, S. M. Schmitt, H. Yang, J. Zuo, D. Fregona and Q. P. Dou, Gold(III)-Dithiocarbamato Peptidomimetics in the Forefront of the Targeted Anticancer Therapy: Preclinical Studies against Human Breast Neoplasia, PLoS One, 2014, 9, e84248.
251. H. J. A. Blaauw, R. J. F. Nivard and G. J. M. van der Kerk, Chemistry of organogold compounds: I. Syntheses and properties of dihalogold(III) N,N-dialkyldithiocarbamates and dialkylgold(III) N,N-dialkyldithiocarbamates, J. Organomet. Chem., 1964, 2, 236–244.
252. R. K. Brown, J. N. Bunyan, A. Agrawal, G. Li, D. Dautoras, J. C. Sarker, T. T. Keat, T. Hicks, G. Hogarth and D. Pugh, A Revised Understanding of the Speciation of Gold(III) Dithiocarbamate Complexes in Solution, Dalton Trans., 2025, 54, 7627–7640.
253. J. Cordón, G. Jiménez-Osés, J. M. López-de-Luzuriaga, M. Monge, M. E. Olmos and D. Pascual, Experimental and Theoretical Study of Gold(III)-Catalyzed Hydration of Alkynes, Organometallics, 2014, 33, 3823–3830.
254. L. Giovagnini, L. Ronconi, D. Aldinucci, D. Lorenzon, S. Sitran and D. Fregona, Synthesis, Characterization, and Comparative in Vitro Cytotoxicity Studies of Platinum(II), Palladium(II), and Gold(III) Methylsarcosinedithiocarbamate Complexes, J. Med. Chem., 2005, 48, 1588–1595.
255. M. Altaf, A. A. Isab, J. Vančo, Z. Dvorák, Z. Trávníček and H. Stoeckli-Evans, Synthesis, characterization and in vitro cytotoxicity of gold(III) dialkyl/diaryldithiocarbamato complexes, RSC Adv., 2015, 5, 81599–81607.
256. O. Loseva, Private communication to the CCDC, deposition number 1977816.
257. A. Angeloski, K. Flower-Donaldson, F. Matar, D. Hayes, M. Duman, D. Oldfield, M. Westerhausen and A. McDonagh, Gold Microstructures by Thermolysis of Gold(III) Di-isopropyldithiocarbamate Complexes, ChemNanoMat, 2024, 10, e202300514.
258. M. Mäkelä, T. HatanpäÄ, K. Mizohata, J. Räisänen, M. Ritala and M. Leskelä, Thermal Atomic Layer Deposition of Continuous and Highly Conducting Gold Thin Films, Chem. Mater., 2017, 29, 6130–6136.
259. M. Contel, A. J. Edwards, J. Garrido, M. B. Hursthouse, M. Laguna and R. Terroba, Mesityl gold(III) complexes. X-ray structure of mononuclear [Au(mes)₂Cl(PPh₃)] and the dimer [Au(mes)₂Cl]₂, J. Organomet. Chem., 2000, 607, 129–136.
260. J. Quero, S. Cabello, T. Fuertes, I. Mármol, R. Laplaza, V. Polo, M. C. Gimeno, J. Rodriguez-Yoldi and E. Cerrada, Proteasome versus Thioredoxin Reductase Competition as Possible Biological Targets in Antitumor Mixed Thiolate-Dithiocarbamate Gold(III) Complexes, Inorg. Chem., 2018, 57, 10832–10845.
261. A. Pettenuzzo, D. Montagner, P. McArdle and L. Ronconi, An innovative and efficient route to the synthesis of metal-based glycoconjugates: proof-of-concept and potential applications, Dalton Trans., 2018, 47, 10721–10736.
262. C. Nardon, D. Fregona, L. Brustolin and N. Pettenuzzo, Coordination compounds, syntheses, nanoformulation and use thereof in oncology, World Intellectual Property Organization, WO2018100561, 2017.
263. S. C. Bajia and A. Mishra, Synthesis and spectroscopic characterization of bis(N-alkyldithiocarbamato)nickel(II) complexes: crystal structures of [Ni(S₂CNH(n-Pr))₂] and [Ni(S₂CNH(i-Pr))₂], J. Coord. Chem., 2011, 64, 2727–2734.
264. A. Z. Halimehjani, K. Marjani, A. Ashouri and V. Amani, Synthesis and characterization of transition metal dithiocarbamate derivatives of 1-aminoadamantane: Crystal structure of (N-adamantyldithiocarbamato)nickel(II), Inorg. Chim. Acta, 2011, 373, 282–285.
265. F. F. Bobinihi, D. C. Onwudiwe, A. C. Ekennia, O. C. Okpareke, C. Arderne and J. R. Lane, Group 10 metal complexes of dithiocarbamates derived from primary anilines: Synthesis, characterization, computational and antimicrobial studies, Polyhedron, 2019, 158, 296–310.
266. C. E. Morrison, F. Wang, N. P. Rath, B. M. Wieliczka, R. A. Loomis and W. E. Buhro, Cadmium Bis(phenyldithiocarbamate) as a Nanocrystal Shell-Growth Precursor, Inorg. Chem., 2017, 56, 12920–12929.
267. L. H. van Poppel, T. L. Groy and M. T. Caudle, Carbon-Sulfur Bond Cleavage in Bis(N-alkyldithiocarbamato)cadmium(II) Complexes: Heterolytic Desulfurization Coupled to Topochemical Proton Transfer, Inorg. Chem., 2004, 43, 3180–3188.
268. A. A. Memon, M. Afzaal, M. A. Malik, C. Q. Nguyen, P. O'Brien and J. Raftery, The N-alkyldithiocarbamato complexes [M(S₂CNHR)₂] (M = Cd(II) Zn(II); R = C₂H₅, C₄H₉, C₆H₁₃, C₁₂H₂₅); their synthesis, thermal decomposition and use to prepare of nanoparticles and nanorods of CdS, Dalton Trans., 2006, 4499–4505.
269. D. C. Onwudiwe, T. Arfin, C. A. Strydom and R. J. Kriek, A study of the thermal and AC impedance properties of N-phenyldithiocarbamate complexes of Zn(II), Electrochim. Acta, 2013, 109, 809–817.
270. B. B. Kaul and K. B. Pandeya, N-Monoaryldithiocarbamatecobalt(III) complexes, Transition Met. Chem., 1979, 4, 112–114.
271. G. L. Zhang, Y. T. Li and Z. Y. Wu, Tris(ethyldithiocarbamato-κ²S,S′)cobalt(III), Acta Crystallogr., Sect. E: Struct. Rep. Online, 2006, 62, m350–m351.
272. E. Tejeria, J. Giglio, L. Fernandez and A. Rey, Development and evaluation of a ^99mTc(V)-nitrido complex derived from estradiol for breast cancer imaging, Appl. Radiat. Isot., 2019, 154, 108854.
273. X. Song, Y. Wang, J. Zhang, Z. Jin, W. Zhang and Y. Zhang, Synthesis and evaluation of a novel ^99mTc nitrido radiopharmaceutical with alendronate dithiocarbamate as a potential bone-imaging agent, Chem. Biol. Drug Des., 2018, 91, 545–551.
274. Y. Chen, H. Guo, F. Xie and J. Lu, Preparation and biological evaluation of ^99mTcN-labeled pteroyl-lys derivative as a potential folate receptor imaging agent, J. Labelled Compd. Radiopharm., 2014, 57, 12–17.
275. N. Hollingsworth, A. Roffey, H. U. Islam, M. Mercy, A. Roldan, W. Bras, M. Wolthers, C. R. A. Catlow, G. Sankar, G. Hogarth and N. H. De Leeuw, Active Nature of Primary Amines during Thermal Decomposition of Nickel Dithiocarbamates to Nickel Sulfide Nanoparticles, Chem. Mater., 2014, 26, 6281–6292.
276. R. Wong and S. J. Dolman, Isothiocyanates from Tosyl Chloride Mediated Decomposition of in Situ Generated Dithiocarbamic Acid Salts, J. Org. Chem., 2007, 72, 3969–3971.
277. N. Sun, B. Li, J. Shao, W. Mo, B. Hu, Z. Shen and X. Hu, A general and facile one-pot process of isothiocyanates from amines under aqueous conditions, Beilstein J. Org. Chem., 2012, 8, 61–70.
278. Z. Fu, W. Yuan, N. Chen, Z. Yang and J. Xu, Na₂S₂O₈-mediated efficient synthesis of isothiocyanates from primary amines in water, Green Chem., 2018, 20, 4484–4491.
279. M. A. Agoro and E. L. Meyer, FeS/FeS₂ nanoscale structures synthesized in one step from Fe(ll) dithiocarbamate complexes as a single source precursor, Front. Chem., 2022, 10, 1035594.
280. A. M. Paca and P. A. Ajibade, Synthesis and structural studies of iron sulphide nanocomposites prepared from Fe(III) dithiocarbamates single source precursors, Mater. Chem. Phys., 2017, 202, 143–150.
281. M. Tarique and M. Aslam, Synthesis and characterization of some transition metal complexes of dithiocarbamate ligand derived from p-toluidine, Asian J. Chem., 2010, 22, 2031–2034.
282. M. A. Agoro and E. L. Meyer, Influence of a One-Pot Approach on a Prepared CuS Macro/Nanostructure from Various Molecular Precursors, Inorganics, 2023, 11, 266.
283. E. I. Duran-Garcia, J. Martinez-Santana, N. Torres-Gomez, A. R. Vilchis-Nestor and I. Garcia-Orozco, Copper sulfide nanoparticles produced by the reaction of N-alkyldithiocarbamatecopper(II) complexes with sodium borohydride, Mater. Chem. Phys., 2021, 269, 124743.
284. N. L. Botha and P. A. Ajibade, Effect of temperature on crystallite sizes of copper sulfide nanocrystals prepared from copper(II) dithiocarbamate single source precursor, Mater. Sci. Semicond. Process., 2016, 43, 149–154.
285. C. Chen, K.-W. Yang, L. Zhai, H.-H. Ding and J.-Z. Chigan, Dithiocarbamates combined with copper for revitalizing meropenem efficacy against NDM-1-producing Carbapenem-resistant Enterobacteriaceae, Bioorg. Chem., 2022, 118, 105474.
286. S. Huang, X. Xu, J. C. Sarker, D. Pugh and G. Hogarth, Primary-amine-derived Cu(I)-dithiocarbamate complexes and their use as low temperature single source precursors to CuS (covellite) nanomaterials, Dalton Trans., 2024, 53, 17140–17145.
287. C. Bianchini, C. A. Ghilardi, A. Meli, S. Midollini and A. Orlandini, Reactivity of copper(I) tetrahydroborates toward carbon disulfide and phenyl isothiocyanate. Structures of (PPh₃)₂Cu(μ-S₂CSCH₂SCS₂)Cu(PPh₃)₂, (PPh₃)₂Cu(S₂COEt), and (PPh₃)₂Cu(S₂CNHPh), Inorg. Chem., 1985, 24, 932–939.
288. Q. Gaydon and S. D. Bohle, Coordination Chemistry of the Parent Dithiocarbamate H₂NCS₂⁻: Organometallic Chemistry and Tris-Chelates of Group 9 Metals, Inorg. Chem., 2022, 61, 4660–4672.
289. C. L. Teske and W. Bensch, On Crystal Structure Investigations of α- and β-Ammoniumdithiocarbamate NH₄CS₂NH₂ and the Role of Hydrogen Bonding, Z. Anorg. Allg. Chem., 2010, 636, 356–362.
290. L. Capacchi, M. Nardelli and A. Villa, The crystal structure of nickel(II) bis(dithiocarbamate), Chem. Commun., 1966, 441.
291. M. A. Bernard, M. M. Borel and J. Gallay, Metal dithiocarbamates. III. Crystallographic study of zinc dithiocarbamate, Bull. Soc. Chim. Fr., 1969, 9, 3069.
292. C. L. Teske and W. Bensch, On Tris(dithiocarbamato)-Chromium(III), Cr(S₂CNH₂)₃, Z. Anorg. Allg. Chem., 2012, 638, 2093–2097.
293. C. L. Raston, A. H. White and A. C. Willis, Crystal structure of tris(dithiocarbamato)cobalt(III), J. Chem. Soc., Dalton Trans., 1975, 2429–2432.
294. C. L. Teske and W. Bensch, On Mono(dithiocarbamato)-silver(I), AgS₂CNH₂, Z. Anorg. Allg. Chem., 2015, 641, 1031–1035.
295. C. L. Teske, H. Reinsch, H. Terraschke and W. Bensch, Synthesis, Crystal Structure and Selected Properties of Mono(dithiocarbamato)-gold(I), AuS₂CNH₂, Z. Anorg. Allg. Chem., 2017, 643, 466–470.
296. C. L. Teske, A.-L. Hansen, R. Weihrich, L. Kienle, M. Kamp, K. P. van der Zwan, J. Senker, C. Dosche, G. Wittstock and W. Bensch, Synthesis, Crystal Structure, and Selected Properties of [Au(S₂CNH₂)₂]SCN: A Precursor for Gold Macro-Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride, Chem. – Eur. J., 2019, 25, 6763–6772.
297. C. L. Teske, On Ammonium-bis(dithiocarbamato)-copper(I)-monohydrate and Mono(dithiocarbamato)-copper(I), Z. Anorg. Allg. Chem., 2013, 639, 2767–2773.
298. M. A. Agoro and E. L. Meyer, Roles of TOPO Coordinating Solvent on Prepared Nano-Flower/Star and Nano-Rods Nickel Sulfides for Solar Cells Applications, Nanomaterials, 2022, 12, 3409.
299. M. A. Agoro and E. L. Meyer, Influence of a One-Pot Approach on a Prepared CuS Macro/Nanostructure from Various Molecular Precursors, Inorganics, 2023, 11, 266.
300. M. A. Agoro, E. L. Meyer and O. I. Olayiwola, Assemble of porous heterostructure thin film through CuS passivation for efficient electron transport in dye-sensitized solar cells, Discover Nano, 2024, 19, 130.
301. M. A. Agoro, E. L. Meyer, J. Z. Mbese and K. Manu, Electrochemical fingerprint of CuS-hexagonal chemistry from (Bis(N-1,4-Phenyl-N-(4-morpholinedithiocarbamato) copper(II) complexes) as photon absorber in quantum-dot/Dye-sensitised solar cells, Catalysts, 2020, 10, 300.
302. M. M. Salman, A. A. Al-Dulaimi, A. S. M. Al-Janabi and M. A. Alheety, Novel dithiocabamate nano Zn(II), Cd(II) and Hg(II) complexes with pyrrolidinedithiocarbamate and N,N-diethyldithiocarbamate, Mater. Today: Proc., 2021, 43, 863–868.
303. P. A. Ajibade, D. C. Onwudiwe and M. J. Moloto, Synthesis of hexadecylamine capped nanoparticles using group 12 complexes of N-alkyl-N-phenyl dithiocarbamate as single-source precursors, Polyhedron, 2011, 30, 246–252.
304. D. C. Onwudiwe and P. A. Ajibade, Synthesis and Crystal Structure of Bis(N-alkyl-N-phenyl dithiocarbamato)mercury(II), J. Chem. Crystallogr., 2011, 41, 980–985.
305. D. C. Onwudiwe, Y. B. Nthwane, A. C. Ekennia and E. Hosten, Synthesis, characterization and antimicrobial properties of some mixed ligand complexes of Zn(II) dithiocarbamate with different N-donor ligands, Inorg. Chim. Acta, 2016, 447, 134–141.
306. P. A. Ajibade and D. C. Onwudiwe, Synthesis and characterization of group 12 complexes of N,N-methyl phenyl-N,N-butyl phenyl dithiocarbamate, J. Coord. Chem., 2011, 64, 2963–2973.
307. E. L. Meyer and M. A. Agoro, Impact of FeS on the TiO₂ Layer As Support System in QDSCs, ACS Omega, 2024, 9, 37891–37900.
308. M. A. Agoro and E. L. Meyer, FeS/FeS₂ nanoscale structures synthesized in one step from Fe(ll) dithiocarbamate complexes as a single source precursor, Front. Chem., 2022, 10, 1035594.
309. M. A. Agoro and E. L. Meyer, Coating of CoS on hybrid anode electrode with enhance performance in hybrid dye-sensitized solar cells, Electrochim. Acta, 2024, 502, 144877.
310. M. A. Agoro, J. Z. Mbese and E. L. Meyer, Inorganic Pb(II)-P and Pb(II)-S Complexes as Photosensitizers from Primary and Secondary Amines in Dyes-Sensitized Solar Cells, ACS Omega, 2021, 6, 23700–23709.
311. M. A. Agoro, J. Z. Mbese and E. L. Meyer, Electrochemistry of Inorganic OCT-PbS/HDA and OCT-PbS Photosensitizers Thermalized from Bis(N-diisopropyl-N-octyldithiocarbamato) Pb(II) Molecular Precursors, Molecules, 2020, 25, 1919.
312. J. Z. Mbese, E. L. Meyer and M. A. Agoro, Electrochemical performance of photovoltaic cells using HDA capped-SnS nanocrystal from bis (N-1,4-phenyl-N-morpho-dithiocarbamato) Sn(II) complexes, Nanomaterials, 2020, 10, 414.
313. E. L. Meyer, J. Z. Mbese, M. A. Agoro and R. Taziwa, Optical and structural-chemistry of SnS nanocrystals prepared by thermal decomposition of bis(N-di-isopropyl-N-octyl dithiocarbamato)tin(II) complex for promising materials in solar cell applications, Opt. Quantum Electron., 2020, 52, 90.
314. J. Z. Mbese, E. L. Meyer and M. A. Agoro, Electrocatalytic properties of PbS nanocrystals structured from (bis(N-1,4-phenyl-N-(4-morpholine)dithiocarbamato Pb(II) complexes) as photosensitizer for quantum-dots-sensitized solar cells, Mater. Lett., 2020, 271, 127770.
315. M. A. Agoro, E. L. Meyer, J. Z. Mbese, X. Fuku and C. C. Ahia, Aliphatic mixed ligands Sn(II) complexes as photon absorbers in quantum dots sensitized solar cell, J. Solid State Chem., 2022, 308, 122890.
316. L. K. Macreadie, C. M. Forsyth, D. R. Turner and A. S. R. Chesman, Cadmium tris(dithiocarbamate) ionic liquids as single source, solvent-free cadmium sulfide precursors, Chem. Commun., 2018, 54, 8925–8928.
317. H. L. M. Van Gaal, J. W. Diesveld, F. W. Pijpers and J. G. M. Van der Linden, Carbon-13 NMR spectra of dithiocarbamates. Chemical shifts, carbon-nitrogen stretching vibration frequencies and π-bonding in the NCS₂ fragment, Inorg. Chem., 1979, 18, 3251–3260.
318. M. Moriyasu and Y. Hashimoto, Kinetic studies of fast equilibrium by high-performance liquid chromatography. I. Ternary complex formation of N,N-disubstituted dithiocarbamate chelates of nickel(II) and copper(II), Bull. Chem. Soc. Jpn., 1980, 53, 3590–3595.
319. M. Moriyasu and Y. Hashimoto, Kinetic studies on the labile ternary nickel(II) chelates of N-disubstituted dithiocarbamic acids by high-performance liquid chromatography, Chem. Lett., 1980, 117–120.
320. M. Moriyasu and Y. Hashimoto, Kinetic studies of fast equilibrium by means of high-performance liquid chromatography. II. Ligand exchange of N,N-disubstituted dithiocarbamate chelates of Ni(II), Bull. Chem. Soc. Jpn., 1981, 54, 2470–2474.
321. O. Liska, G. Guiochon and H. Colin, Liquid chromatography of metal complexes of N-disubstituted dithiocarbamic acids. I. High-performance liquid chromatography of nickel(II) bisdialkyldithiocarbamates, J. Chromatogr., 1979, 171, 145–151.
322. O. Liska, J. Lehotay, E. Brandsteterova and G. Guiochon, Liquid chromatography of metal complexes of N-disubstituted dithiocarbamic acids. II. Identification of nickel(II) bisdialkyldithiocarbamate mixed-ligand complexes, J. Chromatogr., 1979, 171, 153–159.
323. S. Dilli and P. Tong, Liquid chromatography of metal chelates. Chromatographic studies of homologous dialkyldithiocarbamates, Anal. Chim. Acta, 1999, 395, 101–112.
324. E. Beinrohr and J. Garaj, NMR study of ligand exchange in some metal dithiocarbamates, Collect. Czech. Chem. Commun., 1980, 45, 1785–1792.
325. M. Moriyasu and Y. Hashimoto, Kinetic studies of fast equilibrium by means of high-performance liquid chromatography. III. Ternary complex formation between nickel(II) diethyldithiocarbamate and other unlike nickel(II) chelates, Bull. Chem. Soc. Jpn., 1981, 54, 3374–3378.
326. N. V. Duffy, Ligand exchange in tris(diorganodithiocarbamato)iron(III) complexes, Inorg. Chim. Acta, 1981, 47, 31–35.
327. K. Drabent and L. Latos-Grazynski, NMR studies of mixed-ligand iron(III) dithiocarbamates, Polyhedron, 1985, 4, 1637–1641.
328. R. Chant, A. R. Hendrickson, R. L. Martin and N. M. Rohde, Tris(dithiocarbamato) complexes of iron(II), iron(III), and iron(IV). Electrochemical study, Inorg. Chem., 1975, 14, 1894–1902.
329. A. M. Bond, R. Colton, D. Dakternieks, M. L. Dillon, J. Hauenstein and J. E. Moir, Phosphorus-31, cadmium-113 and mercury-199 NMR studies on dithiolate complexes of cadmium and mercury and their phosphine adducts, Aust. J. Chem., 1981, 34, 1393–1400.
330. A. M. Bond, R. Colton, M. L. Dillon, J. E. Moir and D. R. Page, Investigation of exchange and redox reactions of mercury dithiocarbamate complexes by electrochemical techniques at mercury electrodes, mercury-199 nuclear magnetic resonance spectrometry and mass spectrometry, Inorg. Chem., 1984, 23, 2883–2891.
331. M. C. Palazzotto, D. J. Duffy, B. L. Edgar, L. Que Jr and L. H. Pignolet, Dynamic stereochemistry of tris(chelate) complexes. I. Tris(dithiocarbamato) complexes of iron, cobalt, and rhodium, J. Am. Chem. Soc., 1973, 95, 4537–4545.
332. A. R. Hendrickson, R. L. Martin and D. Taylor, Synthesis and properties of dimeric cobalt(III) dithiocarbamate complexes [Co₂(R₂dtc)₅]⁺. X-ray structural analysis of pentakis(diethyldithiocarbamato)dicobalt(III) tetrafluoroborate, J. Chem. Soc., Dalton Trans., 1975, 2182–2188.
333. A. M. Bond, R. Colton, J. E. Moir and D. R. Page, Investigations of mixed-ligand cobalt dithiocarbamate complexes by cobalt-59 nuclear magnetic resonance spectroscopy, mass spectrometry, and electrochemistry, Inorg. Chem., 1985, 24, 1298–1302.
334. F. Artizzu, L. Marchio, L. Pilia, A. Serpe and P. Deplano, Heteroleptic Co(III) bisdithiocarbamato-dithione complexes: Synthesis, structure and bonding of [Co(Et₂dtc)₂(R₂pipdt)]BF₄ (R = Me, 1; Ph, 2; pipdt = piperazin-2,3-dithione) complexes, J. Coord. Chem., 2022, 75, 2434–2447.
335. A. A. Olanrewaju, F. S. Fabiyi, C. U. Ibeji, E. G. Kolawole and R. Gupta, Synthesis, spectral, structure and computational studies of novel transition Metal(II) complexes of (Z)-((dimethylcarbamothioyl)thio) ((1,1,1-trifluoro-4-(naphthalen-2-yl)-4-oxobut-2-en-2-yl)oxy), J. Mol. Struct., 2020, 1211, 128057.
336. A. A. Olanrewaju, C. U. Ibeji and O. E. Oyeneyin, Biological evaluation and molecular docking of some newly synthesized 3d-series metal(II) mixed-ligand complexes of fluoro-naphthyl diketone and dithiocarbamate, SN Appl. Sci., 2020, 2, 678.
337. A. C. Ekennia, D. C. Onwudiwe, L. O. Olasunkanmi, A. A. Osowole and E. E. Ebenso, Synthesis, DFT calculation, and antimicrobial studies of novel Zn(II), Co(II), Cu(II), and Mn(II) heteroleptic complexes containing benzoylacetone and dithiocarbamate, Bioinorg. Chem. Appl., 2015, 1–13.
338. A. C. Ekennia, D. C. Onwudiwe, A. A. Osowole, L. O. Olasunkanmi and E. E. Ebenso, J. Chem., 2016, 5129010.
339. E. V. Ignatov, L. E. Zelenkov, S. V. Baykov, M. K. Shurikov, A. V. Semenov, N. A. Bokach, P. S. Postnikov and V. Yu. Kukushkin, Controlled Mono- and Double-Insertion of Sulfonamide Fragments into Ni–S Bonds of Nickel(II) Dithiocarbamate Complexes via Sulfonyl Azide Reactivity, Inorg. Chem., 2025, 64, 11867–11879.
340. G. Exarchos and S. D. Robinson, Constitution of some “dithiocarbamato-bridged heterobimetallic complexes”, Polyhedron, 1997, 16, 1573–1576.
341. G. Exarchos, S. C. Nyburg and S. D. Robinson, The synthesis and characterization of [Pd(S₂CNEt₂)(Ph₂PCH₂CH₂PPh₂)]⁺ salts of some chloro- and bromo-metalate anions- X-ray crystal structures of [Pd(S₂CNEt₂)(Ph₂PCH₂CH₂PPh₂)]⁺[MCl₂]⁻(M = Cu, Ag), Polyhedron, 1998, 17, 1257–1266.
342. G. Exarchos, S. D. Robinson and J. W. Steed, The synthesis and characterisation of [Pd(S₂CNEt₂){Ph₂P(CH₂)_nPPh₂}]⁺ salts of some chlorometallate anions (n = 1, 3, 4): X-ray crystal structures of the salts [Pd(S₂CNEt₂){Ph₂P(CH₂)_nPPh₂}]₂[MCl₄] (n = 1, 4; M = Cd; n = 3; M = Hg), Polyhedron, 2000, 19, 1511–1517.
343. G. Exarchos, S. D. Robinson and J. W. Steed, The synthesis of new bimetallic complex salts by halide/sulfur chelate cross transfer: X-ray crystal structures of the salts [Ni(S₂CNEt₂)(dppe)]₂[HgBr₄], [Pt(S₂CNEt₂)(dppe)]₂[CdCl₄], [Co(S₂CNEt₂)₂(dppe)]₂ [Cl₃ZnO:(Ph)₂PCH₂CH₂P(Ph)₂:OZnCl₃] and [Pd(S₂CNⁿBu₂)(bipy)]₂[CdCl₄], Polyhedron, 2001, 20, 2951–2963.
344. T. Torimoto, T. Adachi, K.-I. Okazaki, M. Sakuraoka, T. Shibayama, B. Ohtani, A. Kudo and S. Kuwabata, Facile Synthesis of ZnS-AgInS₂ Solid Solution Nanoparticles for a Color-Adjustable Luminophore, J. Am. Chem. Soc., 2007, 129, 12388–12389.
345. T. Kameyama, T. Takahashi, T. Machida, Y. Kamiya, T. Yamamoto, S. Kuwabata and T. Torimoto, Controlling the Electronic Energy Structure of ZnS-AgInS₂ Solid Solution Nanocrystals for Photoluminescence and Photocatalytic Hydrogen Evolution, J. Phys. Chem. C, 2015, 119, 24740–24749.
346. W. Hoisang, T. Uematsu, T. Torimoto and S. Kuwabata, Luminescent Quaternary Ag(In_xGa_1(-x)S₂/GaS_y Core/Shell Quantum Dots Prepared Using Dithiocarbamate Compounds and Photoluminescence Recovery via Post Treatment, Inorg. Chem., 2021, 60, 13101–13109.
347. T. Uematsu, M. Tepakidareekul, T. Hirano, T. Torimoto and S. Kuwabata, Facile High-Yield Synthesis of Ag-In-Ga-S Quaternary Quantum Dots and Coating with Gallium Sulfide Shells for Narrow Band-Edge Emission, Chem. Mater., 2023, 35, 1094–1106.
348. E. J. Mensforth, M. R. Hill and S. R. Batten, Coordination polymers of sulphur-donor ligands, Inorg. Chim. Acta, 2013, 403, 9–24.
349. M. Ebihara, K. Tokoro, M. Maeda, M. Ogami, K. Imaeda, K. Sakurai, H. Masuda and T. Kawamura, Bonding interaction between group 10 and 11 metals. Synthesis, structure and properties of [M₃(S₂CNR₂)₆M’₂]²⁺ (M = Pt or Pd; M′ = Ag or Cu; R = Et, Prⁱ, Prⁿ, Buⁿ or C₆H₁₁), J. Chem. Soc., Dalton Trans., 1994, 3621–3635.
350. J. Fornies, A. Martin, R. Navarro, V. Sicilia, P. Villarroya and A. G. Orpen, Nucleophilic behavior of the neutral complexes [M(C ^{^}P)(S₂CNMe₂)] [M = Pd, Pt; C ^{^}P = CH₂C₆H₄P(C₆H₄Me-o)₂-κ-C,P ] towards Ag(I) and Au(I) compounds. Synthesis (M = Pd, Pt) and molecular structures (M = Pt) of polynuclear complexes containing M-Ag and M-S bonds, J. Chem. Soc., Dalton Trans., 1998, 3721–3726.
351. K. Himoto, T. Horii, S. Oda, S. Suzuki, K. Sugimoto, T. Okubo, M. Maekawa and T. Kuroda-Sowa, Crystal structure of a new mixed-metal coordination polymer consisting of NiII piperidine-dithiocarbamate and pentanuclear CuI-I cluster units, Acta Crystallogr., Sect. E:Crystallogr. Commun., 2018, 74, 233–236.
352. T. Ikada, S. Kuwata, Y. Mizobe and M. Hidai, Syntheses and Structures of Mixed-Metal Sulfido Clusters Containing Incomplete Cubane-Type M₂M′S₄ and Cubane-Type M₂M’₂S₄ Cores (M = Mo, W; M′ = Rh, Ir), Inorg. Chem., 1999, 38, 64–69.
353. H. Brunner, A. Hollman, M. Zabel and B. Nuber, The ligand [Cp₂MoH₂] in complexes with Ag-S bonds, J. Organomet. Chem., 2000, 609, 44–52.
354. K. Ramasamy, M. A. Malik, N. Revaprasadu and P. O'Brien, Routes to Nanostructured Inorganic Materials with Potential for Solar Energy Applications, Chem. Mater., 2013, 25, 3551–3569.
355. K. Ramasamy, M. A. Malik and P. O'Brien, Routes to Copper Zinc Tin Sulfide Cu₂ZnSnS₄ a Potential Material for Solar Cells, Chem. Commun., 2012, 48, 5703–5714.
356. J. A. O. Hill and R. J. Magee, R. J. The Thermochemistry of the Metal Dithiocarbamate and Xanthate Complexes, Rev. Inorg. Chem., 1981, 4, 141–197.
357. J. O. Hill, J. P. Murray and K. C. Patel, The Thermochemistry of the Metal Dithiocarbamate and Xanthate Complexes - A Review Up-date, Rev. Inorg. Chem., 1994, 14, 363–387.
358. A. K. Sharma, Thermal Behaviour of Metal-Dithiocarbamates, Thermochim. Acta, 1986, 104, 339–372.
359. S. K. Sengupta and S. Kumar, Thermal studies on metal dithiocarbamato complexes. A review, Thermochim. Acta, 1984, 72, 349–361.
360. S. T. Breviglieri, E. T. G. Cavalheiro and G. O. Chierice, Correlation Between Ionic Radius and Thermal Decomposition of Fe(II), Co(II), Ni(II), Cu(II) And Zn(II) Diethanoldithiocarbamates, Thermochim. Acta, 2000, 356, 79–84.
361. L. Xi, D. Y. Cho, M. Duchamp, C. B. Boothroyd, J. Y. Lek, A. Besmehn, R. Waser, Y. M. Lam and B. Kardynal, Understanding the Role of Single Molecular ZnS Precursors in the Synthesis of In(Zn)P/ZnS Nanocrystals, ACS Appl. Mater. Interfaces, 2014, 6, 18233–18242.
362. P. B. Mann, I. J. McGregor, S. Bourke, M. Burkitt-Gray, S. Fairclough, M. T. Ma, G. Hogarth, M. Thanou, N. Long and M. Green, An Atom Efficient, Single source Precursor Route to Plasmonic CuS Nanocrystals, Nanoscale Adv., 2019, 1, 522–526.
363. K. Ramasamy, M. A. Malik and P. O'Brien, The Chemical Vapor Deposition of Cu₂ZnSnS₄ Thin Films, Chem. Sci., 2011, 2, 1170–1172.
364. P. Kevin, M. A. Malik, P. O'Brien, J. Cameron, R. G. Taylor, N. J. Findlay, A. R. Inigo and P. J. Skabara, Nanoparticles of Cu₂ZnSnS₄ as Performance Enhancing Additives for Organic Field-Effect Transistors, J. Mater. Chem. C, 2016, 4, 5109–5115.
365. T. Uematsu, M. Tepakidareekul, T. Hirano, T. Torimoto and S. Kuwabata, Facile High-Yield Synthesis of Ag-In-Ga-S Quaternary Quantum Dots and Coating with Gallium Sulfide Shells for Narrow Band-Edge Emission, Chem. Mater., 2023, 35, 1094–1106.
366. W. Hoisang, T. Uematsu, T. Torimoto and S. Kuwabata, Luminescent Quaternary Ag(In_xGa_1(-x)S₂/GaS_y Core/Shell Quantum Dots Prepared Using Dithiocarbamate Compounds and Photoluminescence Recovery via Post Treatment, Inorg. Chem., 2021, 60, 13101–13109.
367. K. S. Ahmad, S. B. Jaffri, H. Panchal, R. K. Gupta, M. A. Abdel-Maksoud, A. Malik and W. H. Al-Qahtani, Advancing energy storage and producing potential with a single source driven semiconducting BaS₃:Cs₂S:La₂S₃ chalcogenide prepared via a sustainable mode, New J. Chem., 2025, 49, 2291–2307.
368. K. S. Ahmad, S. B. Jaffri, K. Chaudhary, R. K. Gupta, G. A. Ashraf and N. H. Alotaibi, Harnessing energy sustainability: synthesis of BaS₂:CoS:MnS semiconductor trichotomous chalcogenide for superior supercapacitor device operation, Ionics, 2025, 31, 2109–2122.
369. K. S. Ahmad, S. B. Jaffri, B. Makawana, R. K. Gupta, G. A. Ashraf and M. Altaf, Sustainable Semiconducting BaS₃:Sb₂S₃:LaS₂ Filiform Rods: Revolutionizing Energy Storage and Production With Mixed Metal Chalcogenides, Appl. Organomet. Chem., 2025, 39, e7880.
370. S. B. Jaffri, K. S. Ahmad, J. S. Al-Hawadi, B. Makawana, R. K. Gupta, G. A. Ashraf and M. K. Okla, Revolutionizing energy storage and electro-catalysis: unleashing electrode power with novel BaS₃:La₂S₃:Ho₂S₃ synthesized from single-source precursors for enhanced electrochemical functionality, J. Sol-Gel Sci. Technol., 2025, 113, 197–212.
371. S. B. Jaffri, K. S. Ahmad, B. Makawana, R. K. Gupta, M. A. Abdel-Maksoud, A. Malik and W. H. Al-Qahtani, Amplifying energy storage and production efficiency: Utilizing BaS₃: Ni₂S₃: Sb₂S₃ synthesized from dithiocarbamate precursors for enhanced and sustainable energy solutions, J. Phys. Chem. Solids, 2025, 196, 112394.
372. R. Yang, J. Nelson, C. Fai, H. A. Yetkin, C. Werner, M. Tervil, A. D. Jess, P. J. Dale and C. J. Hages, A Low-Temperature Growth Mechanism for Chalcogenide Perovskites, Chem. Mater., 2023, 35, 4743–4750.
373. A. E. Dixon, New benzylic derivatives of thiocarbamide, J. Chem. Soc., Dalton Trans., 1891, 59, 551–569.

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