Difference between revisions of "Template:Isocyanidecomplexes"
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| − | # | + | {{Chembox |
| + | <!-- Images --> | ||
| + | | ImageFile = | ||
| + | | ImageFile2 = | ||
| + | <!-- Names --> | ||
| + | | IUPACName = Potassium tetracyanidoborate | ||
| + | | OtherNames = Potassium octacyanoborate | ||
| + | <!-- Sections --> | ||
| + | | Section1 = {{Chembox Identifiers | ||
| + | | index_label = anhydrous | ||
| + | | CASNo = 17456-18-7 | ||
| + | | PubChem = | ||
| + | | SMILES = O.[K+].[K+].[K+].[K+].N#C[Mo-4](C#N)(C#N)(C#N)(C#N)(C#N)(C#N)C#N | ||
| + | | InChI1=1S/8CN.4K.Mo.H2O/c8*1-2;;;;;;/h;;;;;;;;;;;;;1H2/q8*-1;4*+1;+4; | ||
| + | | InChIKey1 = JJVZTQPHXSHIOV-UHFFFAOYSA-N | ||
| + | | SMILES1 = [C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.O.[K+].[K+].[K+].[K+].[Mo+4] | ||
| + | }} | ||
| + | | Section2 = {{Chembox Properties | ||
| + | | Formula = K[B(CN)<sub>4</sub>] | ||
| + | | MolarMass = 153.98 g/mol | ||
| + | | Appearance = white-yellow powder to crystal | ||
| + | | Density = | ||
| + | | MeltingPt = 413 °C<ref name="TCIchemicals">{{TCIchemicals|Product-nr.=P2168|Name=Potassium Tetracyanoborate|Datum=11. april 2019}}.</ref> | ||
| + | | BoilingPt = | ||
| + | | Solubility = | ||
| + | }} | ||
| + | | Section3 = {{Chembox Hazards | ||
| + | | GHSPictograms = {{GHS07}} | ||
| + | | GHSSignalWord = Warning | ||
| + | | HPhrases = {{H-phrases|302|315|319|335}} | ||
| + | | PPhrases = {{P-phrases|261|305+351+338 }} | ||
| + | | MainHazards = | ||
| + | | FlashPt = | ||
| + | | AutoignitionPt = | ||
| + | }} | ||
| + | }} | ||
| + | '''Potassium octacyanomolybdate(IV)''' is the inorganic salt with the formula K<sub>4</sub>[Mo(CN)<sub>8</sub>]. A yellow solid, it is the potassium salt of the homoleptic [[cyanometalate]] with the coordination number eight. The complex [[anion]] consists of a molybdenum cation in the oxidation state IV and eight anionic [[cyanide]] ligands resulting in an overall charge of -4, which is compensated with four potassium cations. K<sub>4</sub>[Mo(CN)<sub>8</sub>] is often found as a dihdydrate. | ||
| + | |||
| + | == Synthesis == | ||
| + | A facile one-pot-synthesis for K<sub>4</sub>[Mo(CN)<sub>8</sub>] · 2 H<sub>2</sub>O is the reduction of [[molybdate]] (MoO<sub>4</sub><sup>2-</sup>) with [[potassium borohydride]] (KBH<sub>4</sub> in a solution with [[potassium cyanide]] and [[acetic acid]]. <ref>J. G. Leipoldt, L. D. C. Bok,P. J. Cilliers, "The preparation of Potassium OctacyanomolybdateIV) Dihydrate", Z. anorg. allg. Chem., 1974, volume 409, pp. 343-44.{{DOI|10.1002/zaac.19744090310}}</ref> This synthesis was one of the first syntheses, where the [[molybdate]] is reduced in the same synthetic step, where the [[cyanometalate]] is formed. The yield is typically about 70%. This synthetic route is useful for big batches, because the work-up is more efficent with more substance and of the inexpensive starting materials compared to the second method. | ||
| + | |||
| + | 4 MoO<sub>4</sub><sup>2-</sup> + 32 CN<sup>-</sup> + BH<sub>4</sub><sup>-</sup> + 31 H<sup>+</sup> → 4 [Mo(CN)<sub>8</sub>]<sup>4-</sup> + 16 H<sub>2</sub>O + H<sub>3</sub>BO<sub>3</sub> | ||
| + | |||
| + | Molybdenum has a high affinity towards [[oxygen]]. To avoid the energy consuming molybdenum-oxygen-bond cleavage, an alternative route to the potassium octacyanotungstate(IV) dihydrate starts from MoCl<sub>4</sub>(Et<sub>2</sub>O)<sub>2</sub> directly from the oxidation state IV, so no reduction is needed in the first step. Also with this route the yield is typically around 70%. <ref>G. Handzlik, M. Magott, B. Sielucka, D. Pinkowicz, "Alternative Synthetic Route to Potassium Octacyanidoniobate(IV ) and I ts Molybdenum Congener", Eur. J. Inorg. Chem., 2016, pp. 4872-77.{{DOI|10.1002/ejic.201600669}}</ref> This synthesis is simpler than the first one and can be made in lower batch sizes than the first synthesis. But the MoCl<sub>4</sub>(Et<sub>2</sub>O)<sub>2</sub> is typically less available than the [[Molybdate]] (MoO<sub>4</sub><sup>2-</sup>). | ||
| + | |||
| + | MoCl<sub>4</sub>(Et<sub>2</sub>O)<sub>2</sub> + 8 KCN → K<sub>4</sub>[Mo(CN)<sub>8</sub>] + 4 KCl + 2 Et<sub>2</sub>O | ||
| + | |||
| + | == Redox Chemistry == | ||
| + | |||
| + | One electron oxidation of the octacyanomolybadate(IV) leads to the paramagnetic octacyanomolybdate(V), which is a 17 electron complex and often used in [[magnetochemistry]]. | ||
| + | |||
| + | == Protonation == | ||
| + | Like many [[cyanometalate]] complexes, octacyanomolybdate(IV) is sensitive towards strong acids.<ref name="Sigma-Aldrich"/> | ||
| + | In strong acids the [[cyanide]] ligands are getting protonated, leading to the corresponding [[hydrogen isocyanide]] ligands. These ligands can be substituted by other ligands e. g., H<sub>2</sub>O. Potonation of [Mo(CN)<sub>8</sub>]<sup>4-</sup> leads to the homoleptic [[hydrogen isocyanide]] complex [Mo(CNH)<sub>8</sub>]<sup>4+</sup>.<ref>M. Sellin, V. Marvaud, M. Malischewski, "Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)<sub>8</sub>]<sup>4+</sup> (M=Mo<sup>IV</sup>, W<sup>IV</sup>) from Superacids", Angew. Chem. Int. Ed., 2020 volume 59, pp. 10519-10522.{{DOI|10.1002/anie.202002366}}</ref> | ||
| + | |||
| + | {{cyanides}} | ||
| + | |||
| + | == References == | ||
| − | + | <references /> | |
| − | + | ||
| − | + | [[Category:Cyano complexes]] | |
| + | [[Category:Coordination compounds]] | ||
| + | [[Category:Molybdenum(IV) compounds]] | ||
| + | [[Category:Potassium compounds]] | ||
| + | [[Category:Coordination compounds]] | ||
Revision as of 16:32, 5 August 2020
| Names | |
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| IUPAC name
Potassium tetracyanidoborate
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| Other names
Potassium octacyanoborate
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| Identifiers | |
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3D model (JSmol)
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| ECHA InfoCard | Script error: No such module "Wikidata". Script error: No such module "Wikidata".Script error: No such module "EditAtWikidata". |
| E number | Script error: No such module "Wikidata". |
CompTox Dashboard (EPA)
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| Properties | |
| K[B(CN)4] | |
| Molar mass | 153.98 g/mol |
| Appearance | white-yellow powder to crystal |
| Melting point | 413 °C[1] |
| Hazards | |
| GHS pictograms | |
| GHS Signal word | Warning [→Category:GHS errors] |
| H302, H315, H319, H335 | |
| Template:P-phrases | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| Infobox references | |
Potassium octacyanomolybdate(IV) is the inorganic salt with the formula K4[Mo(CN)8]. A yellow solid, it is the potassium salt of the homoleptic cyanometalate with the coordination number eight. The complex anion consists of a molybdenum cation in the oxidation state IV and eight anionic cyanide ligands resulting in an overall charge of -4, which is compensated with four potassium cations. K4[Mo(CN)8] is often found as a dihdydrate.
Synthesis
A facile one-pot-synthesis for K4[Mo(CN)8] · 2 H2O is the reduction of molybdate (MoO42-) with potassium borohydride (KBH4 in a solution with potassium cyanide and acetic acid. [2] This synthesis was one of the first syntheses, where the molybdate is reduced in the same synthetic step, where the cyanometalate is formed. The yield is typically about 70%. This synthetic route is useful for big batches, because the work-up is more efficent with more substance and of the inexpensive starting materials compared to the second method.
4 MoO42- + 32 CN- + BH4- + 31 H+ → 4 [Mo(CN)8]4- + 16 H2O + H3BO3
Molybdenum has a high affinity towards oxygen. To avoid the energy consuming molybdenum-oxygen-bond cleavage, an alternative route to the potassium octacyanotungstate(IV) dihydrate starts from MoCl4(Et2O)2 directly from the oxidation state IV, so no reduction is needed in the first step. Also with this route the yield is typically around 70%. [3] This synthesis is simpler than the first one and can be made in lower batch sizes than the first synthesis. But the MoCl4(Et2O)2 is typically less available than the Molybdate (MoO42-).
MoCl4(Et2O)2 + 8 KCN → K4[Mo(CN)8] + 4 KCl + 2 Et2O
Redox Chemistry
One electron oxidation of the octacyanomolybadate(IV) leads to the paramagnetic octacyanomolybdate(V), which is a 17 electron complex and often used in magnetochemistry.
Protonation
Like many cyanometalate complexes, octacyanomolybdate(IV) is sensitive towards strong acids.[4] In strong acids the cyanide ligands are getting protonated, leading to the corresponding hydrogen isocyanide ligands. These ligands can be substituted by other ligands e. g., H2O. Potonation of [Mo(CN)8]4- leads to the homoleptic hydrogen isocyanide complex [Mo(CNH)8]4+.[5]
References
- ↑ Template:TCIchemicals.
- ↑ J. G. Leipoldt, L. D. C. Bok,P. J. Cilliers, "The preparation of Potassium OctacyanomolybdateIV) Dihydrate", Z. anorg. allg. Chem., 1974, volume 409, pp. 343-44.doi:10.1002/zaac.19744090310Template:Only in print
- ↑ G. Handzlik, M. Magott, B. Sielucka, D. Pinkowicz, "Alternative Synthetic Route to Potassium Octacyanidoniobate(IV ) and I ts Molybdenum Congener", Eur. J. Inorg. Chem., 2016, pp. 4872-77.doi:10.1002/ejic.201600669Template:Only in print
- ↑ Cite error: Invalid
<ref>tag; no text was provided for refs namedSigma-Aldrich - ↑ M. Sellin, V. Marvaud, M. Malischewski, "Isolation and Structural Characterization of Eightfold Protonated Octacyanometalates [M(CNH)8]4+ (M=MoIV, WIV) from Superacids", Angew. Chem. Int. Ed., 2020 volume 59, pp. 10519-10522.doi:10.1002/anie.202002366Template:Only in print