| Revision as of 18:31, 12 May 2011 editLamro (talk | contribs)Autopatrolled, Extended confirmed users84,236 edits {{Ruthenium compounds}}← Previous edit |
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| verifiedrevid = 413077086 |
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| verifiedrevid = 428796357 |
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| Name = Ruthenium tetroxide |
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| ImageFile = Ruthenium tetroxide.svg |
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| Name = Ruthenium(VIII) oxide |
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| ImageName = Ruthenium tetroxide |
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| ImageFileL1 = Ruthenium tetroxide.svg |
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| ImageAltL1 = |
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| IUPACName = Ruthenium(VIII) oxide |
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| ImageFileR1 = Ruthenium-tetroxide-3D-balls.png |
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| ImageAltR1 = |
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| Section1 = {{Chembox Identifiers |
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| IUPACName = Ruthenium(VIII) oxide |
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| CASNo = 20427-56-9 |
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| Section1 = {{Chembox Identifiers |
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| PubChem = 119079 |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 20427-56-9 |
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| ChemSpiderID = 106401 |
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| EC_number = 243-813-8 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 97E960G9RP |
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| PubChem = 119079 |
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| InChI = 1S/4O.Ru |
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| InChIKey = GJFMDWMEOCWXGJ-UHFFFAOYSA-N |
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| SMILES = O=(=O)(=O)=O |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = RuO<sub>4</sub> |
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| Formula = RuO<sub>4</sub> |
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| MolarMass = 165.07 g/mol |
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| MolarMass = 165.07 g/mol |
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| Odor = pungent |
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| Odor = pungent |
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| Appearance = colorless liquid |
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| Appearance = yellow easily melting solid |
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| Density = 3.29 g/cm<sup>3</sup> |
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| Density = 3.29 g/cm<sup>3</sup> |
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| Solubility = 2% w/v at 20°C |
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| Solubility = 2% w/v at 20 °C |
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| Solvent = other solvents |
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| Solvent = other solvents |
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| SolubleOther = Soluble in<br />]<br />] |
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| SolubleOther = Soluble in<br />]<br />] |
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| MeltingPtC = |
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| MeltingPt = 25.4 °C |
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| BoilingPtC = 129.6<ref>{{cite journal |last1=Koda |first1=Yoshio |date=1986 |title=Boiling Points and Ideal Solutions of Ruthenium and Osmium Tetraoxides |url= |journal=Journal of the Chemical Society, Chemical Communications |volume=1986 |issue=17 |pages=1347–1348 |doi=10.1039/C39860001347 |access-date=}}</ref> |
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| BoilingPt = 40.0 °C |
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}} |
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| Section3 = {{Chembox Structure |
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| Section3 = {{Chembox Structure |
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| MolShape = tetrahedral |
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| MolShape = tetrahedral |
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| Dipole = zero |
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| Dipole = zero |
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| Section7 = {{Chembox Hazards |
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| Section7 = {{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| NFPA-H = 2 |
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| NFPA-H = 3 |
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| NFPA-F = |
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| NFPA-F = 0 |
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| NFPA-R = |
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| NFPA-R = 1 |
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| Section8 = {{Chembox Related |
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| Section8 = {{Chembox Related |
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| OtherCompounds = ] <br /> ] <br /> ] |
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| OtherCpds = '''RuO<sub>2</sub>'''<br />'''RuCl<sub>3</sub>''' |
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'''Ruthenium tetroxide''' (RuO<sub>4</sub>) is a ] ] ] compound. As expected for a charge-neutral symmetrical ], it is quite volatile. The analogous ] is more widely used and better known. One of the few solvents in which it forms stable solutions is ]. |
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'''Ruthenium tetroxide''' is the ] with the formula RuO<sub>4</sub>. It is a yellow volatile solid that melts near room temperature.<ref name=Brauer>{{cite book|author=H. L. Grube|chapter=Ruthenium (VIII) Oxide|title=Handbook of Preparative Inorganic Chemistry, 2nd Ed. |editor=G. Brauer|publisher=Academic Press|year=1963|place=NY|volume=1|pages=1599–1600}}</ref> It has the odor of ozone.<ref name="Backman_2004" /> Samples are typically black due to impurities. The analogous ] is more widely used and better known. It is also the anhydride of ] (H<sub>2</sub>RuO<sub>5</sub>). One of the few solvents in which RuO<sub>4</sub> forms stable solutions is ].<ref name=EROS>{{Cite book | last1 = Martín | first1 = V. S. | last2 = Palazón | first2 = J. M. | last3 = Rodríguez | first3 = C. M. | last4 = Nevill | first4 = C. R. | chapter = Ruthenium(VIII) Oxide | doi = 10.1002/047084289X.rr009.pub2 | title = Encyclopedia of Reagents for Organic Synthesis | year = 2006 | isbn = 978-0471936237 }}</ref> |
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==Preparation== |
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RuO<sub>4</sub> is prepared by oxidation of ] with ]. |
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== Preparation == |
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:8 Ru<sup>3+</sup> + 5 IO<sub>4</sub><sup>−</sup> + 12 H<sub>2</sub>O → 8 RuO<sub>4</sub> + 5 I<sup>−</sup> + 24 H<sup>+</sup> |
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RuO<sub>4</sub> is prepared by oxidation of ] with ].<ref /name=Brauer/> The reaction initially produces sodium diperiodo­dihydroxo­ruthenate(VI), which then decomposes in acid solution to the tetroxide:<ref>{{cite journal|pages=777–778|journal=J. Inorg. Nucl. Chem.|year=1972|volume=34|publisher=]|location=Great Britain|title=A periodate complex of ruthenium(VI)|orig-date=1 July 1971|first1=E. E.|last1=Mercer|first2=S. M.|last2=Meyer|issue=2 |doi=10.1016/0022-1902(72)80466-4}}</ref> |
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<!--equation assumes reduction of periodate produces iodide, rather than (say) iodine or hypoiodite--> |
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:8 Ru<sup>3+</sup>(aq) + 5 IO<sub>4</sub><sup>−</sup>(aq) + 12 H<sub>2</sub>O(l) → 8 RuO<sub>4</sub>(s) + 5 I<sup>−</sup>(aq) + 24 H<sup>+</sup>(aq)<ref>{{Cite journal |last1=Carlsen |first1=Per H. J. |last2=Katsuki |first2=Tsutomu |last3=Martin |first3=Victor S. |last4=Sharpless |first4=K. Barry |date=September 1981 |title=A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds |url=https://pubs.acs.org/doi/abs/10.1021/jo00332a045 |journal=The Journal of Organic Chemistry |language=en |volume=46 |issue=19 |pages=3936–3938 |doi=10.1021/jo00332a045 |issn=0022-3263}}</ref> |
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In typical reactions featuring RuO<sub>4</sub> as the oxidant, many forms of ruthenium usefully serve as precursors to RuO<sub>4</sub>, such as oxide hydrates or hydrated ]. |
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<!--equation assumes reduction of periodate produces iodide, rather than (say) iodine or iodate--> |
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Due to its challenging reactivity, RuO<sub>4</sub> is always generated ''in situ'' and used in catalytic quantities, at least in organic reactions.<ref name=EROS/> |
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Because RuO<sub>4</sub> will readily decompose explosively at slightly elevated temperatures, most laboratories do not synthesize it directly, nor is it commercially available through major chemical vendors. Most laboratories instead use an anionic derivative from a salt of "TPAP" (]), RuO<sub>4</sub>. TPAP is synthesized by oxidizing RuCl<sub>3</sub> to RuO<sub>4</sub><sup><nowiki>−</nowiki></sup> by ] and countering it with the tetrapropylamine cation. |
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==Properties and uses== |
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== Structure == |
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RuO<sub>4</sub> forms two crystal structures, one with ] symmetry and another with ] symmetry, isotypic to OsO<sub>4</sub>. The molecule adopts a ] geometry, with the Ru–O distances ranging from 169 to 170 pm.<ref>{{ cite journal |author1=Pley, M. |author2=Wickleder, M. S. | title = Two Crystalline Modifications of RuO<sub>4</sub> | journal = Journal of Solid State Chemistry | year = 2005 | volume = 178 | issue = 10 | pages = 3206–3209 | doi = 10.1016/j.jssc.2005.07.021 |bibcode=2005JSSCh.178.3206P }}</ref> |
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RuO<sub>4</sub> oxidizes virtually any hydrocarbon. For example, it will oxidize ] to 1-adamantanol. It is used in ] to oxidize terminal ] to 1,2-]s and primary ] to ]. When used in this fashion, the ruthenium tetroxide is used in catalytic amounts and regenerated by the addition of ] to ] and a ] mixture of ], ] and ]. |
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==Uses== |
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Because it is such an aggressive oxidant, reaction conditions are mild, generally room temperature. Although a strong oxidant, RuO<sub>4</sub> oxidations do not perturb ]s that are not oxidized. Illustrative is the oxidation of the following diol to a ]: |
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===Isolation of ruthenium from ores=== |
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The main commercial value of RuO<sub>4</sub> is as an intermediate in the production of ruthenium compounds and metal from ores. Like other ] (PGMs), ] occurs at low concentrations and often mixed with other PGMs. Together with OsO<sub>4</sub>, it is separated from other PGMs by distillation of a chlorine-oxidized extract. Ruthenium is separated from OsO<sub>4</sub> by reducing RuO<sub>4</sub> with ], a process that exploits the highly positive reduction potential for the <sup>0/-</sup> couple.<ref>{{cite journal | doi = 10.1016/j.reactfunctpolym.2005.05.011| title = A review of methods of separation of the platinum-group metals through their chloro-complexes| journal = Reactive and Functional Polymers| volume = 65| issue = 3| pages = 205–217| year = 2005| last1 = Bernardis| first1 = Francesco L.| last2 = Grant| first2 = Richard A.| last3 = Sherrington| first3 = David C.}}</ref><ref>{{cite journal|author1=Swain, P. |author2=Mallika, C. |author3=Srinivasan, R. |author4=Mudali, U. K. |author5=Natarajan, R. |title=Separation and recovery of ruthenium: a review|journal=Journal of Radioanalytical and Nuclear Chemistry |year=2013|volume=298|issue=2|pages=781–796|doi=10.1007/s10967-013-2536-5|s2cid=95804621}}</ref> |
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===Organic chemistry=== |
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RuO<sub>4</sub> is of specialized value in organic chemistry because it oxidizes virtually any hydrocarbon.<ref>{{cite journal |last1=Vincenzo |first1=Piccialli |title=Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species |journal=Molecules |date=2014 |volume=19 |issue=5 |pages=6534–6582 |doi=10.3390/molecules19056534 |doi-access=free |pmid=24853716 |pmc=6270930 }}</ref> For example, it will oxidize ] to 1-adamantanol. Because it is such an aggressive oxidant, reaction conditions must be mild, generally room temperature. Although a strong oxidant, RuO<sub>4</sub> oxidations do not perturb ]s that are not oxidized. Illustrative is the oxidation of the following diol to a ]: |
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Oxidation of ] alcohols also occurs without degradation of the epoxide ring: |
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Oxidation of ] alcohols also occurs without degradation of the epoxide ring: |
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Under milder conditions, oxidative reaction yields ]s instead. RuO<sub>4</sub> readily converts secondary alcohols into ]. Although similar results can be achieved with other cheaper ]s such as ]- or ]-based oxidants, RuO<sub>4</sub> is ideal when a very vigorous oxidant is needed, but mild conditions must be maintained. It is used in ] to oxidize internal ] to 1,2-]s, and terminal alkynes along with primary ] to ]. When used in this fashion, the ruthenium(VIII) oxide is used in catalytic amounts and regenerated by the addition of ] to ] and a ] mixture of ], ] and ]. RuO<sub>4</sub> readily cleaves double bonds to yield ] products, in a manner similar to ]. ], a more familiar oxidant that is structurally similar to RuO<sub>4</sub>, does not cleave double bonds, instead producing ] diol products. However, with short reaction times and carefully controlled conditions, RuO<sub>4</sub> can also be used for dihydroxylation.<ref>{{Cite journal|last=Plietker|first=Bernd|year=2005|title=Selectivity versus reactivity - recent advances in RuO4-catalyzed oxidations|journal=Synthesis |volume=5|issue=15|pages=2453–2472|doi=10.1055/s-2005-872172}}</ref> |
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Under milder condition, oxidative reaction yields ]s instead. |
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Because RuO<sub>4</sub> degrades the "double bonds" of arenes (especially electron-rich ones) by dihydroxylation and cleavage of the C-C bond in a way few other reagents can, it is useful as a "deprotection" reagent for carboxylic acids that are masked as aryl groups (typically phenyl or ''p''-methoxyphenyl). Because the fragments formed are themselves readily oxidizable by RuO<sub>4</sub>, a substantial fraction of the arene carbon atoms undergo exhaustive oxidation to form carbon dioxide. Consequently, multiple equivalents of the terminal oxidant (often in excess of 10 equivalents per aryl ring) are required to achieve complete conversion to the carboxylic acid, limiting the practicality of the transformation.<ref>{{Cite journal|last1=Nunez|first1=M. Teresa|last2=Martin|first2=Victor S.|date=March 1990|title=Efficient oxidation of phenyl groups to carboxylic acids with ruthenium tetraoxide. A simple synthesis of (R)-.gamma.-caprolactone, the pheromone of Trogoderma granarium|journal=The Journal of Organic Chemistry|volume=55|issue=6|pages=1928–1932|doi=10.1021/jo00293a044|issn=0022-3263}}</ref><ref>{{Cite journal|last1=Nasr|first1=Khaled|last2=Pannier|first2=Nadine|last3=Frangioni|first3=John V.|last4=Maison|first4=Wolfgang|date=February 2008|title=Rigid Multivalent Scaffolds Based on Adamantane|journal=The Journal of Organic Chemistry|volume=73|issue=3|pages=1056–1060|doi=10.1021/jo702310g|issn=0022-3263|pmc=2505186|pmid=18179237}}</ref><ref>{{Cite journal|date=2003-02-17|title=Oxidative degradation of benzene rings|journal=Tetrahedron|volume=59|issue=8|pages=1105–1136|doi=10.1016/S0040-4020(02)01492-8|issn=0040-4020|last1=Mander|first1=Lewis N.|last2=Williams|first2=Craig M.}}</ref> |
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RuO<sub>4</sub> readily converts secondary alcohols into ]. Although similar results can be achieved with other cheaper ]s such as ]- or ]-based oxidants, RuO<sub>4</sub> is ideal when a very vigorous oxidant is needed but mild conditions must be maintained. |
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] |
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RuO<sub>4</sub> readily cleaves double bonds to yield ] products, in a manner similar to ]. ], a more familiar oxidant that is structurally similar to RuO<sub>4</sub>, does not cleave double bonds, instead producing ] diol products. |
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Although used as a direct ], due to the relatively high cost of RuO<sub>4</sub> it is also used ] with a cooxidant. For an oxidation of cyclic ] with RuO<sub>4</sub> as a catalyst and ] as oxidant under ] conditions, RuO<sub>4</sub> is first activated by hydroxide, turning into the hyperruthenate anion: |
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In terms of practical details, the substrate to be oxidized is typically dissolved in solvent such as ], and ] is added as an aiding ] to the catalytic cycle. ] can then be added to precipitate and recover the ruthenium pre-catalyst. |
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==Oxidative catalyst and mechanism== |
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Although used as a direct ], due to the relatively high cost of RuO<sub>4</sub> it is also used ] with an associated re-oxidant. For an oxidation of cyclic ] with RuO<sub>4</sub> as a catalyst and ] as a ], RuO<sub>4</sub> is first activated by hydroxide: |
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:RuO<sub>4</sub> + OH<sup>−</sup> → HRuO<sub>5</sub><sup>−</sup> |
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:RuO<sub>4</sub> + OH<sup>−</sup> → HRuO<sub>5</sub><sup>−</sup> |
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The reaction proceeds via a glycolate complex. |
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===Other uses=== |
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Then HRuO<sub>5</sub><sup>−</sup> complexes with the cyclic alcohol and form a metal coordination complex (denoted C<sub>1</sub> here): |
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Ruthenium tetroxide is a potential staining agent. It is used to expose latent fingerprints by turning to the brown/black ruthenium dioxide when in contact with fatty oils or fats contained in sebaceous contaminants of the print.<ref>{{ cite journal |author1=Mashiko, K. |author2=Miyamoto, T. | title = Latent Fingerprint Processing by the Ruthenium Tetroxide Method | journal = Journal of Forensic Identification | year = 1998 | volume = 48 | issue = 3 | pages = 279–290 | doi = 10.3408/jasti.2.21 | url = https://www.ncjrs.gov/App/publications/abstract.aspx?ID=172645 | doi-access = free }}</ref> |
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== Gaseous release by nuclear accidents == |
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:HRuO<sub>5</sub><sup>−</sup> + (CH<sub>2</sub>CH<sub>2</sub>)<sub>''n''</sub>CHOH → C<sub>1</sub> + OH<sup>−</sup> |
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Because of the very high volatility of ruthenium tetroxide ({{chem|Ru|O|4}}) ] with their relative short half-life are considered as the second most hazardous gaseous isotopes after ] in case of release by a nuclear accident.<ref name="Ronneau_1995">{{Cite journal|url=https://doi.org/10.1016/0265-931X(95)91633-F|doi=10.1016/0265-931X(95)91633-F|title=Oxidation-enhanced emission of ruthenium from nuclear fuel|year=1995|last1=Ronneau|first1=C.|last2=Cara|first2=J.|last3=Rimski-Korsakov|first3=A.|journal=Journal of Environmental Radioactivity|volume=26|pages=63–70}}</ref><ref name="Backman_2004">Backman, U., Lipponen, M., Auvinen, A., Jokiniemi, J., & Zilliacus, R. (2004). . Final report (No. NKS–100). Nordisk Kernesikkerhedsforskning.</ref><ref name="Beuzet_2012">{{Cite journal |title=Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code |journal=Nuclear Engineering and Design |volume=246 |pages=157–162 |last1=Beuzet |first1=Emilie |last2=Lamy |first2=Jean-Sylvestre |last3=Perron |first3=Hadrien |last4=Simoni |first4=Eric |last5=Ducros |first5=Gérard |doi=10.1016/j.nucengdes.2011.08.025 |year=2012 }}</ref> The two most important radioactive ] are <sup>103</sup>Ru and <sup>106</sup>Ru. They have half-lives of 39.6 days and 373.6 days, respectively.<ref name="Backman_2004" /> |
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The Ru complex is then attracted by a bromate in which the oxidation of the coordinated alcohol take place: |
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== References == |
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:C<sub>1</sub> + BrO<sub>3</sub><sup>−</sup> → (CH<sub>2</sub>CH<sub>2</sub>)<sub>''n''</sub>C=O + HRuO<sub>5</sub><sup>−</sup> |
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{{reflist}} |
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== Further reading == |
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In which HRuO<sub>5</sub><sup>−</sup> is reformed as the ], and the cyclic alcohol is oxidized into a cyclic ]. |
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* {{cite book |last1=Cotton |first1=S.A. |title=Chemistry of Precious Metals |year=1997 |publisher=Chapman and Hall |location=London |isbn=978-0-7514-0413-5}} |
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* {{Cite journal | last1 = Farmer | first1 = V. | last2 = Welton | first2 = T. | doi = 10.1039/B109851A | title = The oxidation of alcohols in substituted imidazolium ionic liquids using ruthenium catalysts | journal = Green Chemistry | volume = 4 | issue = 2 | pages = 97 | year = 2002 }} |
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* {{Cite journal | last1 = Singh | first1 = B. | last2 = Srivastava | first2 = S. | doi = 10.1007/BF01129466 | title = Kinetics and mechanism of ruthenium tetroxide catalysed oxidation of cyclic alcohols by bromate in a base | journal = Transition Metal Chemistry | volume = 16 | issue = 4 | pages = 466 | year = 1991 | s2cid = 95711945 }} |
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* {{cite journal |last1= Courtney|first1= J.L.|last2= Swansbor|first2= K.F.|year= 1972|title= Ruthenium tetroxide oxidation|journal= Reviews of Pure and Applied Chemistry|volume= 22|page= 47}} |
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{{Ruthenium compounds}} |
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==Staining== |
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{{Oxides}} |
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Ruthenium tetroxide can be used as an even more aggressive form of ] for the study of polymers by ] than ]. It has the advantage of staining even polyethylene, the disadvantage is that it is not very selective in what it stains. |
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==References== |
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{{Citation style|date=September 2007}} |
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{{reflist}} |
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* Cotton, S. A. "Chemistry of Precious Metals," Chapman and Hall (London): 1997. ISBN 0-7514-0413-6 |
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* Martin, V. S., Palazón, J. M., 'Ruthenium(VIII) Oxide', ''Encyclopedia of Reagents for Organic Synthesis'' '''2001'''. () |
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*Farmer, V., Welton, T., The oxidation of alcohols in substituted imidazolium ionic liquids using ruthenium catalysts ''Royal Society of Chemistry'', '''2002'''. |
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*Singh, B., Srivastava, S., Kinetics and Mechanism of Ruthenium tetroxide Catalysed Oxidation of Cyclic Alcohols by Bromate in a Base ''Transition Met. Chem.'', '''1991''', 16, 466-468. |
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*Courtney, JL., Swansbor, KF. Ruthenium tetroxide Oxidation ''Reviews of Pure and Applied Chemistry '''1972''', 22, 47- |
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{{Ruthenium compounds}} |
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{{DEFAULTSORT:Ruthenium Tetroxide}} |
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