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Transition metal dithiocarbamate complexes

Transition metal dithiocarbamate complexes is a science topic covered in the lgStudy science library. This page brings together a partial reference excerpt, illustrations, worked examples, real-world applications and a short study plan, so you can understand Transition metal dithiocarbamate complexes rather than just read about it. In short: Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc−. Many complexes are known.

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Reference excerpt

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc−. Many complexes are known. Several homoleptic derivatives have the formula M(R2dtc)n where n = 2, 3 and 4.

Ligand characteristics

Dithiocarbamate anions, when bidentate, are classified as L–X ligands in the Covalent bond classification method. In the usual electron counting method, they are three-electron ligands. With respect to HSAB theory, they are classified as soft. Being intermediate in terms of ligand field strength, they form ferric complexes exhibit spin-crossover behavior. Because of the pi-donor properties of the amino substituents, the two sulfur centers show enhanced basicity relative to dithiocarboxylates. This situation is represented by the zwitterionic resonance structure that depicts a positive charge on N and negative charges on both sulfurs. This N-to-C pi-bonding results in partial double bond character for the C–N bond. Consequently, barriers to rotational about this bond are elevated. Another consequence of their high basicity, dithiocarbamates often stabilize complexes in some high oxidation states (e.g., Fe(IV), Co(IV), Ni(III), Cu(III)). Dithiocarbamate salts are easily synthesized by treating secondary amines with carbon disulfide in the presence of sodium hydroxide:

R2NH + CS2 + NaOH → R2NCS−2Na+ + H2O A wide variety of secondary amines give the corresponding dtc ligands. Popular amines include dimethylamine (Me2NH), diethylamine (Et2NH), and pyrrolidine ((CH2)4NH). Complexes of H2NCS−2, derived from the parent dithiocarbamic acid have been reported.

Related ligands

Dithiocarbamates are classified as derivatives of dithiocarbamic acid. Their properties as ligands resemble the conjugate bases of many related "1,1-dithioacids":

Diorganothiophosphates, (RO)2PS−2 Dithiocarboxylates, RCS−2 Xanthates, ROCS−2 Thioxanthates, RSCS−2 Diselenocarbamates, R2NCSe−2, such as diethyldiselenocarbamate

Synthetic methods Commonly, metal dithiocarbamates are prepared by salt metathesis reactions using alkali metal dithiocarbamates:

NiCl2 + 2 NaS2CNMe2 → Ni(S2CNMe2)2 + 2 NaCl In some cases, the dithiocarbamate serves as a reductant, followed by its complexation. A complementary method entails oxidative addition of thiuram disulfides to low-valent metal complexes:

Mo(CO)6 + 2 [S2CNMe2]2 → Mo(S2CNMe2)4 + 6 CO Metal amido complexes, such as tetrakis(dimethylamido)titanium, react with carbon disulfide:

Ti(NMe2)4 + 4 CS2 → Ti(S2CNMe2)4

Homoleptic complexes

Bis complexes nickel bis(dimethyldithiocarbamate), palladium bis(dimethyldithiocarbamate), platinum bis(dimethyldithiocarbamate), all square-planar complexes copper bis(diethyldithiocarbamate), a square-planar complex Tris complexes vanadium tris(diethyldithiocarbamate), an octahedral complex chromium tris(diethyldithiocarbamate), an octahedral complex manganese tris(dimethyldithtiocarbamate), an octahedral complex iron tris(diethyldithiocarbamate), ruthenium tris(diethyldithiocarbamate), osmium tris(diethyldithiocarbamate), all octahedral complexes cobalt tris(diethyldithiocarbamate), rhodium tris(diethyldithiocarbamate), iridium tris(diethyldithiocarbamate), all octahedral complexes Tetrakis complexes titanium tetrakis(dimethyldithiocarbamate) molybdenum tetrakis(diethyldithiocarbamate) Dimetallic complexes iron bis(diethyldithiocarbamate), pentacoordinate Fe dimer zinc bis(dimethyldithiocarbamate), pentacoordinate Zn dimer dicobalt pentakis(diethyldithiocarbamate) cation, with a pair of octahedral Co(III) centers diruthenium pentakis(diethyldithiocarbamate) cation, with a pair of octahedral Ru(III) centers, two isomers

Reactions Dithiocarbamate ligand can be removed from complexes by oxidation, as illustrated by the iodination of the iron tris(diethyldithiocarbamate):

2 Fe(S2CNEt2)3 + I2 → 2 Fe(S2CNEt2)2I + (S2CNEt2)2 They degrade to metal sulfides upon heating.

Applications Dtc complexes find several applications:

herbicides in the form of the iron and zinc derivatives Ferbam and Zineb, respectively vulcanization accelerators, zinc bis(dimethyldithiocarbamate). biochemistry, iron tris(dimethyldithiocarbamate) for detection of nitric oxide. lubricants. Metal thiocarbamates are also used in metal-to-metal lubrication proposes, mainly as an anti-oxidation or anti-extreme pressure (EP) additive. 1%–2% of such compounds can be added to internal combustion engine lubricant to increase extreme pressure performance in high operational temperatures.

History Délepine appears to have first prepared transition metal dithiocarbamate complexes in the form of copper(II) derivatives. A century earlier, complexes of xanthates has been reported by William Christopher Zeise. The phenomenon of spin crossover was reported in 1931 by Cambi et al. who observed anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes. The spin states of these complexes were sensitive to the nature of the amine substituents.

References

Illustrations

Worked examples

Example 1 — a first encounter with Transition metal dithiocarbamate complexes

Start with the simplest possible case. Write down what Transition metal dithiocarbamate complexes claims or describes in one sentence, then invent the smallest concrete situation in which that sentence is true. In science, the smallest case is usually a single object, a single equation or a single measurement. Check that every symbol or term in your sentence has a meaning in that case.

Example 2 — changing one variable

Take the situation from Example 1 and change exactly one quantity: double it, halve it, or set it to zero. Predict what should happen to Transition metal dithiocarbamate complexes before you calculate. Comparing your prediction with the result is the fastest way to find out whether you understand the idea or only the words.

Example 3 — an exam-style question

Typical questions about Transition metal dithiocarbamate complexes ask you to (a) state it precisely, (b) apply it to given data, and (c) explain a limitation. Practise writing all three answers in under five minutes; the third part is what separates a full-mark answer from an average one.

Applications of Transition metal dithiocarbamate complexes

In research: Transition metal dithiocarbamate complexes appears in science research whenever the underlying quantities have to be modelled precisely. Papers usually cite it as a starting assumption and then explore where it breaks down.
In technology and industry: Engineering practice reuses Transition metal dithiocarbamate complexes in design rules, simulations and safety margins. Knowing the idea lets you read a specification sheet and understand why the numbers look the way they do.
In the classroom: Transition metal dithiocarbamate complexes is common in secondary-school and first-year university syllabi. It links to neighbouring topics Dithiocarbamates, so understanding it makes those chapters shorter.
In everyday life: Look for Transition metal dithiocarbamate complexes outside the textbook — in sport, cooking, traffic, electronics or the sky above you. An example you found yourself is remembered far longer than one you were given.

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Frequently asked questions

What is Transition metal dithiocarbamate complexes in simple terms?

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc−. Many complexes are known.

Why does Transition metal dithiocarbamate complexes matter?

Because it connects several science ideas at once: it gives you a definition you can apply, a quantity you can calculate, and a way to check whether a result is plausible.

How should I study Transition metal dithiocarbamate complexes?

Read the excerpt, restate it from memory, then work through the examples and applications listed on this page. The five-step study plan above takes about twenty minutes.

What does this page cover?

It gives you a compact reference excerpt plus original lgStudy explanations, examples, applications and study material on Transition metal dithiocarbamate complexes.