Ammonium tetrathiomolybdate

Last updated
Ammonium tetrathiomolybdate
Ammonium Tetrathiomolybdate.jpg
Names
Other names
ammonium thiomolybdate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.167.865 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
RTECS number
  • QA4668250
UNII
  • InChI=1S/Mo.2H3N.4S/h;2*1H3;;;;/q;;;;;2*-1/p+2 Yes check.svgY
    Key: PQNOIAHNKHBLRN-UHFFFAOYSA-P Yes check.svgY
  • InChI=1S/Mo.2H3N.4S/h;2*1H3;;;;/q;;;;;2*-1/p+2
  • Key: PQNOIAHNKHBLRN-UHFFFAOYSA-P
  • [NH4+].[NH4+].[S-][Mo]([S-])(=S)=S
Properties
(NH4)2MoS4
Molar mass 260.28 g/mol
Appearancered crystals
Melting point decomp ~ 155 °C [1]
Basicity (pKb)decomposes
Structure
[2]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
toxic
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Related compounds
Related compounds
(NH4)2[WS4],
MoS2
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Ammonium tetrathiomolybdate is the chemical compound with the formula (NH4)2MoS4. This bright red ammonium salt is an important reagent in the chemistry of molybdenum and has been used as a building block in bioinorganic chemistry. The thiometallate (see metallate) anion has the distinctive property of undergoing oxidation at the sulfur centers concomitant with reduction of the metal from Mo(VI) to Mo(IV).

Contents

Preparation and structure

The salt contains the tetrahedral [MoS4]2− anion. The compound is prepared by treating solutions of molybdate, [MoO4]2− with hydrogen sulfide in the presence of ammonia: [3]

(NH4)2MoO4 + 4 H2S → (NH4)2MoS4 + 4 H2O
The [MoS4] anion. MoS4.png
The [MoS4] anion.

Reactions

The anion is also an excellent ligand. For example, with Ni(II) sources, it forms [Ni(MoS4)2]2−. Much of the chemistry of the thiomolybdate results from studies on salts of quaternised organic cations, such as [NEt4]2[MoS4] and [PPh4]2[MoS4] (Et = C2H5, Ph = C6H5). [4] These organic salts are soluble in polar organic solvents such as acetonitrile and dmf.

The thermal decomposition of [NH4]2[MoS4] leads to molybdenum trisulfide (MoS3), ammonia (NH3) and hydrogen sulfide (H2S), beginning at 155 °C till 280 °C. [1]

(NH4)2MoS4 → MoS3 + 2 NH3 + H2S

MoS3 then decomposes again to molybdenum disulfide (MoS2) in a broad temperature range from 300 °C to 820 °C. Perfect decomposition to MoS2 under inert gas requires at least 800 °C according to the following reaction,

MoS3 → MoS2 + S

but it can also be achieved at 450 °C, if there is enough hydrogen. [5]

MoS3 + H2 → MoS2 + H2S

Several related thio and seleno anions are known including (A = alkali metal cation, [PPh4]+, [NEt4]+)

More complex tetrahedral anions include A2[MoS4−xOx] and A2[WS4−xOx]

Uses

Ammonium tetrathiomolybdate was first used therapeutically in the treatment of copper toxicosis in animals. It was then introduced as a treatment in Wilson's disease, a hereditary copper metabolism disorder, in humans; it acts both by competing with copper absorption in the bowel and by increasing excretion. Clinical studies have shown ATTM can effectively lower copper levels faster than currently available treatments, and that fewer patients with an initial neurological presentation of their disease who are treated with ATTM experience neurological deterioration [14] [15] [16]

Various phase II clinical trial of ATTM for copper depletion in cancer have been performed. [17]

ATTM has also been found to have an inhibitory effect on angiogenesis, potentially via the inhibition of Cu ion dependent membrane translocation process involving a non-classical secretion pathway. [18] This makes it an interesting investigatory treatment for cancer, age-related macular degeneration, and other diseases featuring excessive blood vessel deposition. [14]

Related Research Articles

<span class="mw-page-title-main">Ammonium</span> Chemical compound

The ammonium cation is a positively charged polyatomic ion with the chemical formula NH+4 or [NH4]+. It is formed by the protonation of ammonia. Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations, where one or more hydrogen atoms are replaced by organic or other groups.

<span class="mw-page-title-main">Bisulfide</span> Inorganic anion containing one sulfur and one hydrogen atoms

Bisulfide is an inorganic anion with the chemical formula HS−. It contributes no color to bisulfide salts, and its salts may have a distinctive putrid smell. It is a strong base. Bisulfide solutions are corrosive and attack the skin.

Classical qualitative inorganic analysis is a method of analytical chemistry which seeks to find the elemental composition of inorganic compounds. It is mainly focused on detecting ions in an aqueous solution, therefore materials in other forms may need to be brought to this state before using standard methods. The solution is then treated with various reagents to test for reactions characteristic of certain ions, which may cause color change, precipitation and other visible changes.

<span class="mw-page-title-main">Ammonium hydrosulfide</span> Chemical compound

Ammonium hydrosulfide is the chemical compound with the formula [NH4]SH.

<span class="mw-page-title-main">Sodium thioantimoniate</span> Chemical compound

Sodium thioantimoniate or sodium tetrathioantimonate(V) is an inorganic compound with the formula Na3SbS4. The nonahydrate of this chemical, Na3SbS4·9H2O, is known as Schlippe's salt, named after Johann Karl Friedrich von Schlippe (1799–1867). These compounds are examples of sulfosalts. They were once of interest as species generated in qualitative inorganic analysis.

<span class="mw-page-title-main">Ammonium bifluoride</span> Chemical compound

Ammonium bifluoride is the inorganic compound with the formula [NH4][HF2] or [NH4]F·HF. It is produced from ammonia and hydrogen fluoride. This colourless salt is a glass-etchant and an intermediate in a once-contemplated route to hydrofluoric acid.

<span class="mw-page-title-main">Vanadium(III) fluoride</span> Chemical compound

Vanadium(III) fluoride is the chemical compound with the formula VF3. This yellow-green, refractory solid is obtained in a two-step procedure from V2O3. Similar to other transition-metal fluorides (such as MnF2), it exhibits magnetic ordering at low temperatures (e.g. V2F6.4H2O orders below 12 K).

<span class="mw-page-title-main">Silicon disulfide</span> Chemical compound

Silicon disulfide is the inorganic compound with the formula SiS2. Like silicon dioxide, this material is polymeric, but it adopts a 1-dimensional structure quite different from the usual forms of SiO2.

<span class="mw-page-title-main">Ammonium dichromate</span> Chemical compound

Ammonium dichromate is an inorganic compound with the formula (NH4)2Cr2O7. In this compound, as in all chromates and dichromates, chromium is in a +6 oxidation state, commonly known as hexavalent chromium. It is a salt consisting of ammonium ions and dichromate ions.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]−. It is an octahedral species that imparts no color to its salts. [PF6]− is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]−. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

Molybdenum dioxide is the chemical compound with the formula MoO2. It is a violet-colored solid and is a metallic conductor. The mineralogical form of this compound is called tugarinovite, and is only very rarely found.

<span class="mw-page-title-main">Molybdenum blue</span> Pigment

Molybdenum blue is a term applied to:

<span class="mw-page-title-main">Ammonium thiocyanate</span> Chemical compound

Ammonium thiocyanate is an inorganic compound with the formula [NH4]+[SCN]−. It is an ammonium salt of thiocyanic acid. It consists of ammonium cations [NH4]+ and thiocyanate anions [SCN]−.

<span class="mw-page-title-main">Molybdate</span> Chemical compound of the form –O–MoO₂–O–

In chemistry, a molybdate is a compound containing an oxyanion with molybdenum in its highest oxidation state of 6: O−−Mo(=O)2−O−. Molybdenum can form a very large range of such oxyanions, which can be discrete structures or polymeric extended structures, although the latter are only found in the solid state. The larger oxyanions are members of group of compounds termed polyoxometalates, and because they contain only one type of metal atom are often called isopolymetalates. The discrete molybdenum oxyanions range in size from the simplest MoO2−
4, found in potassium molybdate up to extremely large structures found in isopoly-molybdenum blues that contain for example 154 Mo atoms. The behaviour of molybdenum is different from the other elements in group 6. Chromium only forms the chromates, CrO2−
4, Cr
2O2−
7, Cr
3O2−
10 and Cr
4O2−
13 ions which are all based on tetrahedral chromium. Tungsten is similar to molybdenum and forms many tungstates containing 6 coordinate tungsten.

<span class="mw-page-title-main">Trisulfur</span> Chemical compound

The S3 molecule, known as trisulfur, sulfur trimer, thiozone, or triatomic sulfur, is a cherry-red allotrope of sulfur. It comprises about 10% of vaporised sulfur at 713 K and 1,333 Pa. It has been observed at cryogenic temperatures as a solid. Under ordinary conditions it converts to cyclooctasulfur.

Ammonium orthomolybdate is the inorganic compound with the chemical formula (NH4)2MoO4. It is a white solid that is prepared by treating molybdenum trioxide with aqueous ammonia. Upon heating these solutions, ammonia is lost, to give ammonium heptamolybdate ((NH4)6Mo7O24·4H2O).

<span class="mw-page-title-main">Ammonium carbamate</span> Chemical compound

Ammonium carbamate is a chemical compound with the formula [NH4][H2NCO2] consisting of ammonium cation NH+4 and carbamate anion NH2COO−. It is a white solid that is extremely soluble in water, less so in alcohol. Ammonium carbamate can be formed by the reaction of ammonia NH3 with carbon dioxide CO2, and will slowly decompose to those gases at ordinary temperatures and pressures. It is an intermediate in the industrial synthesis of urea (NH2)2CO, an important fertilizer.

Ammonium dimolybdate (ADM) is the inorganic compound with the formula (NH4)2Mo2O7. It is a white, water-soluble solid. ADM is an intermediate in the production of molybdenum compounds from its ores. Roasting typical ore produces crude molybdenum(VI) oxides, which can be extracted into aqueous ammonia, affording ammonium molybdate. Heating solutions of ammonium molybdate gives ADM. Upon heating, solid ammonium dimolybdate decomposes to molybdenum trioxide:

Lanthanide trichlorides are a family of inorganic compound with the formula LnCl3, where Ln stands for a lanthanide metal. The trichlorides are standard reagents in applied and academic chemistry of the lanthanides. They exist as anhydrous solids and as hydrates.

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +4, and +3 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. The tetrathioperrhenate anion [ReS4]− is possible.

References

  1. 1 2 Prasad, TP; Diemann, E; Müller, A (1973). "Thermal decomposition of (NH4)2MoO2S2, (NH4)2MoS4, (NH4)2WO2S2 and (NH4)2WS4". Journal of Inorganic and Nuclear Chemistry . 35 (6): 1895. doi:10.1016/0022-1902(73)80124-1.
  2. ↑ Hill, B; Lerner, H-W; Bolte, M (2010). "Redetermination of diammonium thiomolybdate" (PDF). Acta Crystallographica E . 66 (13): i13. Bibcode:2010AcCrE..66I..13H. doi: 10.1107/S1600536810003016 . PMC   2979694 . PMID   21579587.
  3. ↑ Müller, A; Diemann, E; Jostes, R; Bögge, H (1981). "Transition metal thio anions: Properties and significance for complex chemistry and bioinorganic chemistry". Angewandte Chemie International Edition in English . 20 (11): 934. doi:10.1002/anie.198109341.
  4. ↑ Coucouvanis, D (1998). "Syntheses, structures, and reactions of binary and tertiary thiomolydate complexes containing the (O)Mo(Sx) and (S)Mo(Sx) functional groups (x = 1, 2, 4)". Advances in Inorganic Chemistry . 45: 1–73. doi:10.1016/S0898-8838(08)60024-0. ISBN   978-0-12-023645-9.
  5. ↑ Brito, JL; Ilija, M; Hernández, P (1995). "Thermal and reductive decomposition of ammonium thiomolybdates". Thermochimica Acta . 256 (2): 325. doi:10.1016/0040-6031(94)02178-Q.
  6. 1 2 3 Lee, SC; Li, J; Mitchell, JC; Holm, RH (1992). "Group 5 tetrathiometalates: Simplified syntheses and structures". Inorg. Chem. 31 (21): 4333–4338. doi:10.1021/ic00047a021.
  7. 1 2 Prasad, T. P.; Müller, A. (1976). "Thermal decompositions of (NH4)2WSe4 and (NH4)3VS4 under normal and reduced nitrogen pressures". Journal of Thermal Analysis . 10: 396–373. doi:10.1021/jo00032a019.
  8. ↑ Srinivasan, BR; Poisot, M; Näther, C; Bensch, W (2004). "Diammonium tetrathiotungstate(VI), [NH4]2[WS4], at 150 K". Acta Crystallographica E . E60 (11): i136–8. Bibcode:2004AcCrE..60I.136S. doi:10.1107/S1600536804023761.
  9. ↑ Hunyadi, Dávid; Machado Ramos, Ana Luisa Vieira; Szilágyi, Imre Miklós (2015). "Thermal decomposition of ammonium tetrathiotungstate". Journal of Thermal Analysis and Calorimetry . 120: 209–215. doi: 10.1007/s10973-016-5353-6 .
  10. ↑ Dhar, Preeti; Chidambaram, Nallaperumal; Chandrasekaran, Srinivasan (1992). "Piperidinium tetrathiotungstate as sulfur transfer reagent: synthesis of cyclic disulfides". The Journal of Organic Chemistry . 57 (6): 1699–1702. doi:10.1021/jo00032a019.
  11. ↑ Sureshkumar, Devarajulu; Gunasundari, Thanikachalam; Saravanan, Vadivelu; Chandrasekaran, Srinivasan (2007). "Tetraselenotungstate: an efficient selenating reagent for the synthesis of β-amino diselenides by aziridine ring opening reactions". Tetrahedron Letters . 48 (4): 623–626. doi:10.1016/j.tetlet.2006.11.118.
  12. ↑ Goodman, JT; Rauchfuss, TB (2002). "Useful Reagents and Ligands". Inorganic Syntheses. Inorganic Syntheses. Vol. 33. pp. 107–110. doi:10.1002/0471224502.ch2. ISBN   0471208256.
  13. ↑ Compound Summary for Bis-choline tetrathiomolybdate
  14. 1 2 Brewer, GJ; Hedera, P; Kluin, KJ; Carlson, M; et al. (2003). "Treatment of Wilson disease with ammonium tetrathiomolybdate: III. Initial therapy in a total of 55 neurologically affected patients and follow-up with zinc therapy". Arch Neurol. 60 (3): 379–85. doi: 10.1001/archneur.60.3.379 . PMID   12633149.
  15. ↑ Brewer, GJ; Askari, F; Lorincz, MT; Carlson, M; et al. (2006). "Treatment of Wilson disease with ammonium tetrathiomolybdate: IV. Comparison of tetrathiomolybdate and trientine in a double-blind study of treatment of the neurologic presentation of Wilson disease". Arch Neurol. 63 (4): 521–7. doi: 10.1001/archneur.63.4.521 . PMID   16606763.
  16. ↑ Brewer, GJ; Askari, F; Dick, RB; Sitterly, J; et al. (2009). "Treatment of Wilson's disease with tetrathiomolybdate: V. Control of free copper by tetrathiomolybdate and a comparison with trientine". Translational Research . 154 (2): 70–7. doi:10.1016/j.trsl.2009.05.002. PMID   19595438.
  17. ↑ Lopez, Jay; Ramchandani, Divya; Vahdat, Linda (2019). "Chapter 12. Copper Depletion as a Therapeutic Strategy in Cancer". In Sigel, Astrid; Freisinger, Eva; Sigel, Roland K. O.; Carver, Peggy L. (Guest editor) (eds.). Essential Metals in Medicine:Therapeutic Use and Toxicity of Metal Ions in the Clinic. Vol. 19. Berlin: de Gruyter GmbH. pp. 267–301. doi:10.1515/9783110527872-018. ISBN   978-3-11-052691-2. PMID   30855113. S2CID   73727976.{{cite book}}: |editor4-first= has generic name (help); |journal= ignored (help)
  18. ↑ Nickel, W (2003). "The Mystery of nonclassical protein secretion, a current view on cargo proteins and potential export routes". Eur. J. Biochem. 270 (10): 2109–2119. doi: 10.1046/j.1432-1033.2003.03577.x . PMID   12752430.
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