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| Section3 = {{Chembox Structure |
| Section3 = {{Chembox Structure |
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| Coordination = |
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| CrystalStruct = {{cite journal |author=B. Hill, H.-W. Lerner and M. Bolte |title= |journal=[[Acta Crystallographica E]] |volume=66 |year=2010 |issue=13 |doi=10.1107/S1600536810003016}} |
| CrystalStruct = {{cite journal |author=B. Hill, H.-W. Lerner and M. Bolte |title= Redetermination of diammonium thiomolybdate|journal=[[Acta Crystallographica E]] |volume=66 |year=2010 |issue=13 |pages= i13|doi=10.1107/S1600536810003016}} |
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| Section7 = {{Chembox Hazards |
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==Related compounds== |
==Related compounds== |
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Several related thio and seleno anions are known including (A = alkali metal cation, [PPh<sub>4</sub>]<sup>+</sup>, [NEt<sub>4</sub>]<sup>+</sup>) |
Several related thio and seleno anions are known including (A = alkali metal cation, [PPh<sub>4</sub>]<sup>+</sup>, [NEt<sub>4</sub>]<sup>+</sup>) |
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*A<sub>3</sub>[VS<sub>4</sub>]<ref name=Lee1>{{cite journal |
*A<sub>3</sub>[VS<sub>4</sub>]<ref name=Lee1>{{cite journal | title = Group 5 Tetrathiometalates: Simplified Syntheses and Structures | journal = [[Inorg. Chem.]] | year = 1992 | volume = 31 | pages = 4333–4338 | doi = 10.1021/ic00047a021 | issue = 21| author-separator = ; |author1 = Lee|first1 = S. C.|last2 = Li| first2 = J. | last3 = Mitchell | first3 = J. C. | last4 = Holm | first4 = R. H.]] | authorlink4 = Richard h. Holm }}</ref> |
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*A<sub>3</sub>[NbS<sub>4</sub>]<ref name=Lee1/> |
*A<sub>3</sub>[NbS<sub>4</sub>]<ref name=Lee1/> |
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*A<sub>3</sub>[TaS<sub>4</sub>]<ref name=Lee1/> |
*A<sub>3</sub>[TaS<sub>4</sub>]<ref name=Lee1/> |
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*A<sub>2</sub>[WS<sub>4</sub>]<ref>{{cite journal | author = Srinivasan, B. R.; Poisot, M.; Näther, C.; Bensch, W. | title = Diammonium tetrathiotungstate(VI), [NH<sub>4</sub>]<sub>2</sub>[WS<sub>4</sub>], at 150 K | journal = [[Acta Crystallographica E]] | year = 2004 | volume = E60 | pages = i136–i138 | doi = 10.1107/S1600536804023761 | issue = 11}}</ref> |
*A<sub>2</sub>[WS<sub>4</sub>]<ref>{{cite journal | author = Srinivasan, B. R.; Poisot, M.; Näther, C.; Bensch, W. | title = Diammonium tetrathiotungstate(VI), [NH<sub>4</sub>]<sub>2</sub>[WS<sub>4</sub>], at 150 K | journal = [[Acta Crystallographica E]] | year = 2004 | volume = E60 | pages = i136–i138 | doi = 10.1107/S1600536804023761 | issue = 11}}</ref> |
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*A<sub>2</sub>[WSe<sub>4</sub>] |
*A<sub>2</sub>[WSe<sub>4</sub>] |
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*A[ReS<sub>4</sub>]<ref>{{cite journal | author = Goodman, J. T.; Rauchfuss, T. B., | title = Tetraethylammonium-tetrathioperrhenate [Et<sub>4</sub>N][ReS<sub>4</sub>] | journal = [[Inorganic Syntheses]] | year = 2002 | volume = 33 | pages = 107–110 | doi=10.1002/0471224502.ch2}}</ref> |
*A[ReS<sub>4</sub>]<ref>{{cite journal | author = Goodman, J. T.; Rauchfuss, T. B., | title = Tetraethylammonium-tetrathioperrhenate [Et<sub>4</sub>N][ReS<sub>4</sub>] | journal = [[Inorganic Syntheses]] | year = 2002 | volume = 33 | pages = 107–110 | doi=10.1002/0471224502.ch2| isbn = 0471208256 }}</ref> |
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*MoS<sub>4</sub><sup>2-</sup> ([[Bis-choline tetrathiomolybdate]])<ref>[http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=18442052 Compound Summary for Bis-choline tetrathiomolybdate]</ref> |
*MoS<sub>4</sub><sup>2-</sup> ([[Bis-choline tetrathiomolybdate]])<ref>[http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=18442052 Compound Summary for Bis-choline tetrathiomolybdate]</ref> |
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More complex tetrahedral anions include A<sub>2</sub>[MoS<sub>4-x</sub>O<sub>x</sub>] and A<sub>2</sub>[WS<sub>4-x</sub>O<sub>x</sub>] |
More complex tetrahedral anions include A<sub>2</sub>[MoS<sub>4-x</sub>O<sub>x</sub>] and A<sub>2</sub>[WS<sub>4-x</sub>O<sub>x</sub>] |
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==Uses== |
==Uses== |
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Ammonium tetrathiomolybdate was first used therapeutically in the treatment of [[copper toxicosis]] in animals. It was then introduced as a [[Bis-choline tetrathiomolybdate|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 <ref>Brewer GJ, Hedera P, Kluin KJ, Carlson M, Askari F, Dick RB, Sitterly J, Fink JK, 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''': 379-385.</ref><ref>Brewer GJ, Askari F, Lorincz, MT, Carlson M, Schilsky M, Kluin KJ, Hedera P, Moretti P, Fink JK, Tankanow R, Dick RB, Sitterly J, 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''': 521-527.</ref><ref>{{cite journal |last1= Brewer |first1= GJ |last2= Askari |first2= F |last3= Dick |first3= RB |last4= Sitterly |first4= J |last5= Fink |first5= JK |last6= Carlson |first6= M |last7= Kluin |first7= KJ |last8= Lorincz |first8= MT |displayauthors= 4 |year= 2009 |title= Treatment of Wilson's disease with tetrathiomolybdate: V. Control of free copper by tetrathiomolybdate and a comparison with trientine |journal= [[Translational Research (journal)|Translational Research |volume= 154 |pages= |
Ammonium tetrathiomolybdate was first used therapeutically in the treatment of [[copper toxicosis]] in animals. It was then introduced as a [[Bis-choline tetrathiomolybdate|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 <ref>Brewer GJ, Hedera P, Kluin KJ, Carlson M, Askari F, Dick RB, Sitterly J, Fink JK, 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''': 379-385.</ref><ref>Brewer GJ, Askari F, Lorincz, MT, Carlson M, Schilsky M, Kluin KJ, Hedera P, Moretti P, Fink JK, Tankanow R, Dick RB, Sitterly J, 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''': 521-527.</ref><ref>{{cite journal |last1= Brewer |first1= GJ |last2= Askari |first2= F |last3= Dick |first3= RB |last4= Sitterly |first4= J |last5= Fink |first5= JK |last6= Carlson |first6= M |last7= Kluin |first7= KJ |last8= Lorincz |first8= MT |displayauthors= 4 |year= 2009 |title= Treatment of Wilson's disease with tetrathiomolybdate: V. Control of free copper by tetrathiomolybdate and a comparison with trientine |journal= [[Translational Research (journal)|Translational Research |volume= 154 |pages= 70–7}}</ref> |
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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.<ref>{{cite journal | author = Nickel, W. | title = The Mystery of nonclassical protein secretion, a current view on cargo proteins and potential export routes | journal = [[Eur. J. Biochem.]] | year = 2003 | volume = 270 | pages = 2109–2119 | doi = 10.1046/j.1432-1033.2003.03577.x | pmid = 12752430 | issue = 10 }}</ref> This makes it an interesting investigatory treatment for [[cancer]], [[age-related macular degeneration]], and other diseases featuring excessive blood vessel deposition.<ref>{{cite journal|author=Brewer, G. J.; Hedera, P.; Kluin, K. J. |
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.<ref>{{cite journal | author = Nickel, W. | title = The Mystery of nonclassical protein secretion, a current view on cargo proteins and potential export routes | journal = [[Eur. J. Biochem.]] | year = 2003 | volume = 270 | pages = 2109–2119 | doi = 10.1046/j.1432-1033.2003.03577.x | pmid = 12752430 | issue = 10 }}</ref> This makes it an interesting investigatory treatment for [[cancer]], [[age-related macular degeneration]], and other diseases featuring excessive blood vessel deposition.<ref>{{cite journal|author=Brewer, G. J.; Hedera, P.; Kluin, K. J. |title=Treatment of Wilson disease with ammonium tetrathiomolybdate: III. Initial therapy in a total of 55 neurologically affected patients and follow-up with zinc therapy |journal=Arch Neurol |year=2003 |volume=60 |issue=3 |pages=379–85 |pmid=12633149 |url= http://archneur.ama-assn.org/cgi/content/full/60/3/379 |doi=10.1001/archneur.60.3.379|displayauthors=1 }}</ref> |
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==References== |
==References== |
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Revision as of 04:42, 27 December 2014
| Names | |
|---|---|
| Other names
ammonium thiomolybdate
| |
| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
| ECHA InfoCard | 100.167.865 |
| RTECS number |
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CompTox Dashboard (EPA)
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| |
| |
| Properties | |
| H8N2MoS4 | |
| Molar mass | 260.28 g/mol |
| Appearance | red crystals |
| Melting point | decomp ~ 155 °C[1] |
| Basicity (pKb) | decomposes |
| Structure | |
| B. Hill, H.-W. Lerner and M. Bolte (2010). "Redetermination of diammonium thiomolybdate". Acta Crystallographica E. 66 (13): i13. doi:10.1107/S1600536810003016. | |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
|
toxic |
| Related compounds | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
| |
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 anion has the distinctive property of undergoing oxidation at the sulfur centers concomitant with reduction of the metal from Mo(VI) to Mo(IV).
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:[2]
- [NH4]2[MoO4] + 4 H2S → [NH4]2[MoS4] + 4 H2O
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).[3] 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)2(MoS4) → 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.[4]
- MoS3 + H2 → MoS2 + H2S
Related compounds
Several related thio and seleno anions are known including (A = alkali metal cation, [PPh4]+, [NEt4]+)
- A3[VS4][5]
- A3[NbS4][5]
- A3[TaS4][5]
- A2[MoSe4]
- A2[WS4][6]
- A2[WSe4]
- A[ReS4][7]
- MoS42- (Bis-choline tetrathiomolybdate)[8]
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 [9][10][11]
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.[12] This makes it an interesting investigatory treatment for cancer, age-related macular degeneration, and other diseases featuring excessive blood vessel deposition.[13]
References
- ^ a b Prasad, T. P.; 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.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - ^ 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.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - ^ 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. Advances in Inorganic Chemistry. 45: 1–73. doi:10.1016/S0898-8838(08)60024-0. ISBN 978-0-12-023645-9.
{{cite journal}}:|chapter=ignored (help) - ^ Brito, J. L. ; 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.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - ^ a b c Lee, S. C.; Li, J.; Mitchell, J. C.; Holm, R. H.]] (1992). "Group 5 Tetrathiometalates: Simplified Syntheses and Structures". Inorg. Chem. 31 (21): 4333–4338. doi:10.1021/ic00047a021.
{{cite journal}}: Unknown parameter|author-separator=ignored (help) - ^ Srinivasan, B. R.; Poisot, M.; Näther, C.; Bensch, W. (2004). "Diammonium tetrathiotungstate(VI), [NH4]2[WS4], at 150 K". Acta Crystallographica E. E60 (11): i136–i138. doi:10.1107/S1600536804023761.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - ^ Goodman, J. T.; Rauchfuss, T. B., (2002). "Tetraethylammonium-tetrathioperrhenate [Et4N][ReS4]". Inorganic Syntheses. 33: 107–110. doi:10.1002/0471224502.ch2. ISBN 0471208256.
{{cite journal}}: CS1 maint: extra punctuation (link) CS1 maint: multiple names: authors list (link) - ^ Compound Summary for Bis-choline tetrathiomolybdate
- ^ Brewer GJ, Hedera P, Kluin KJ, Carlson M, Askari F, Dick RB, Sitterly J, Fink JK, 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: 379-385.
- ^ Brewer GJ, Askari F, Lorincz, MT, Carlson M, Schilsky M, Kluin KJ, Hedera P, Moretti P, Fink JK, Tankanow R, Dick RB, Sitterly J, 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: 521-527.
- ^ {{cite journal |last1= Brewer |first1= GJ |last2= Askari |first2= F |last3= Dick |first3= RB |last4= Sitterly |first4= J |last5= Fink |first5= JK |last6= Carlson |first6= M |last7= Kluin |first7= KJ |last8= Lorincz |first8= MT |displayauthors= 4 |year= 2009 |title= Treatment of Wilson's disease with tetrathiomolybdate: V. Control of free copper by tetrathiomolybdate and a comparison with trientine |journal= [[Translational Research (journal)|Translational Research |volume= 154 |pages= 70–7}}
- ^ 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.
- ^ Brewer, G. J.; Hedera, P.; Kluin, K. J. (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.
{{cite journal}}: Unknown parameter|displayauthors=ignored (|display-authors=suggested) (help)CS1 maint: multiple names: authors list (link)