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Ruthenium tetroxide

January 01, 1970

Ruthenium tetroxide is the inorganic compound with the formula RuO4. It is a yellow volatile solid that melts near room temperature.[2] It has the odor of ozone.[3] Samples are typically black due to impurities. The analogous OsO4 is more widely used and better known. It is also the anhydride of hyperruthenic acid (H2RuO5). One of the few solvents in which RuO4 forms stable solutions is CCl4.[4]

Ruthenium(VIII) oxide
Names
IUPAC name
Ruthenium(VIII) oxide
Identifiers
  • 20427-56-9 Y
3D model (JSmol)
  • Interactive image
ChemSpider
  • 106401
ECHA InfoCard 100.039.815
EC Number
  • 243-813-8
  • 119079
UNII
  • 97E960G9RP Y
  • DTXSID20174373
  • InChI=1S/4O.Ru
    Key: GJFMDWMEOCWXGJ-UHFFFAOYSA-N
  • O=[Ru](=O)(=O)=O
Properties
RuO4
Molar mass 165.07 g/mol
Appearance yellow easily melting solid
Odor pungent
Density 3.29 g/cm3
Boiling point 129.6[1] °C (265.3 °F; 402.8 K)
2% w/v at 20 °C
Solubility in other solvents Soluble in
Carbon tetrachloride
Chloroform
Structure
tetrahedral
zero
Hazards
NFPA 704 (fire diamond)
Health 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
0
1
Safety data sheet (SDS) external MSDS sheet
Related compounds
Related compounds
 Ruthenium dioxide
Ruthenium trichloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)

Preparation edit

RuO4 is prepared by oxidation of ruthenium(III) chloride with NaIO4.[2] The reaction initially produces sodium diperiodo­dihydroxo­ruthenate(VI), which then decomposes in acid solution to the tetroxide:[5]

8 Ru3+(aq) + 5 IO4−(aq) + 12 H2O(l) → 8 RuO4(s) + 5 I−(aq) + 24 H+(aq)[6]

Due to its challenging reactivity, RuO4 it is always generated in situ and used in catalytic quantities, at least in organic reactions.[4]

Structure edit

RuO4 forms two crystal structures, one with cubic symmetry and another with monoclinic symmetry, isotypic to OsO4. The molecule adopts a tetrahedral geometry, with the Ru–O distances ranging from 169 to 170 pm.[7]

Uses edit

Isolation of ruthenium from ores edit

The main commercial value of RuO4 is as an intermediate in the production of ruthenium compounds and metal from ores. Like other platinum group metals (PGMs), ruthenium occurs at low concentrations and often mixed with other PGMs. Together with OsO4, it is separated from other PGMs by distillation of a chlorine-oxidized extract. Ruthenium is separated from OsO4 by reducing RuO4 with hydrochloric acid, a process that exploits the highly positive reduction potential for the [RuO4]0/- couple.[8][9]

Organic chemistry edit

RuO4 is of specialized value in organic chemistry because it oxidizes virtually any hydrocarbon. For example, it will oxidize adamantane to 1-adamantanol. Because it is such an aggressive oxidant, reaction conditions must be mild, generally room temperature. Although a strong oxidant, RuO4 oxidations do not perturb stereocenters that are not oxidized. Illustrative is the oxidation of the following diol to a carboxylic acid:

 

Oxidation of epoxy alcohols also occurs without degradation of the epoxide ring:

 

Under milder conditions, oxidative reaction yields aldehydes instead. RuO4 readily converts secondary alcohols into ketones. Although similar results can be achieved with other cheaper oxidants such as PCC- or DMSO-based oxidants, RuO4 is ideal when a very vigorous oxidant is needed, but mild conditions must be maintained. It is used in organic synthesis to oxidize internal alkynes to 1,2-diketones, and terminal alkynes along with primary alcohols to carboxylic acids. When used in this fashion, the ruthenium(VIII) oxide is used in catalytic amounts and regenerated by the addition of sodium periodate to ruthenium(III) chloride and a solvent mixture of acetonitrile, water and carbon tetrachloride. RuO4 readily cleaves double bonds to yield carbonyl products, in a manner similar to ozonolysis. OsO4, a more familiar oxidant that is structurally similar to RuO4, does not cleave double bonds, instead producing vicinal diol products. However, with short reaction times and carefully controlled conditions, RuO4 can also be used for dihydroxylation.[10]

Because RuO4 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 RuO4, 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.[11][12][13]

 

Although used as a direct oxidant, due to the relatively high cost of RuO4 it is also used catalytically with a cooxidant. For an oxidation of cyclic alcohols with RuO4 as a catalyst and bromate as oxidant under basic conditions, RuO4 is first activated by hydroxide, turning into the hyperruthenate anion:

RuO4 + OH− → HRuO5−

The reaction proceeds via a glycolate complex.

Other uses edit

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.[14]

Gaseous release by nuclear accidents edit

Because of the very high volatility of ruthenium tetroxide (RuO
4) ruthenium radioactive isotopes with their relative short half-life are considered as the second most hazardous gaseous isotopes after iodine-131 in case of release by a nuclear accident.[15][3][16] The two most important radioactive isotopes of ruthenium are 103Ru and 106Ru. They have half-lives of 39.6 days and 373.6 days, respectively.[3]

References edit

  1. ^ Koda, Yoshio (1986). "Boiling Points and Ideal Solutions of Ruthenium and Osmium Tetraoxides". Journal of the Chemical Society, Chemical Communications. 1986 (17): 1347–1348. doi:10.1039/C39860001347.
  2. ^ a b H. L. Grube (1963). "Ruthenium (VIII) Oxide". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY: Academic Press. pp. 1599–1600.
  3. ^ a b c Backman, U., Lipponen, M., Auvinen, A., Jokiniemi, J., & Zilliacus, R. (2004). Ruthenium behaviour in severe nuclear accident conditions. Final report (No. NKS–100). Nordisk Kernesikkerhedsforskning.
  4. ^ a b Martín, V. S.; Palazón, J. M.; Rodríguez, C. M.; Nevill, C. R. (2006). "Ruthenium(VIII) Oxide". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rr009.pub2. ISBN 978-0471936237.
  5. ^ Mercer, E. E.; Meyer, S. M. (1972) [1 July 1971]. "A periodate complex of ruthenium(VI)". J. Inorg. Nucl. Chem. 34 (2). Great Britain: Pergamon: 777–778. doi:10.1016/0022-1902(72)80466-4.
  6. ^ Carlsen, Per H. J.; Katsuki, Tsutomu; Martin, Victor S.; Sharpless, K. Barry (September 1981). "A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds". The Journal of Organic Chemistry. 46 (19): 3936–3938. doi:10.1021/jo00332a045. ISSN 0022-3263.
  7. ^ Pley, M.; Wickleder, M. S. (2005). "Two Crystalline Modifications of RuO4". Journal of Solid State Chemistry. 178 (10): 3206–3209. Bibcode:2005JSSCh.178.3206P. doi:10.1016/j.jssc.2005.07.021.
  8. ^ Bernardis, Francesco L.; Grant, Richard A.; Sherrington, David C. (2005). "A review of methods of separation of the platinum-group metals through their chloro-complexes". Reactive and Functional Polymers. 65 (3): 205–217. doi:10.1016/j.reactfunctpolym.2005.05.011.
  9. ^ Swain, P.; Mallika, C.; Srinivasan, R.; Mudali, U. K.; Natarajan, R. (2013). "Separation and recovery of ruthenium: a review". Journal of Radioanalytical and Nuclear Chemistry. 298 (2): 781–796. doi:10.1007/s10967-013-2536-5. S2CID 95804621.
  10. ^ Plietker, Bernd (2005). "Selectivity versus reactivity - recent advances in RuO4-catalyzed oxidations". Synthesis. 5 (15): 2453–2472. doi:10.1055/s-2005-872172.
  11. ^ Nunez, M. Teresa; Martin, Victor S. (March 1990). "Efficient oxidation of phenyl groups to carboxylic acids with ruthenium tetraoxide. A simple synthesis of (R)-.gamma.-caprolactone, the pheromone of Trogoderma granarium". The Journal of Organic Chemistry. 55 (6): 1928–1932. doi:10.1021/jo00293a044. ISSN 0022-3263.
  12. ^ Nasr, Khaled; Pannier, Nadine; Frangioni, John V.; Maison, Wolfgang (February 2008). "Rigid Multivalent Scaffolds Based on Adamantane". The Journal of Organic Chemistry. 73 (3): 1056–1060. doi:10.1021/jo702310g. ISSN 0022-3263. PMC 2505186. PMID 18179237.
  13. ^ Mander, Lewis N.; Williams, Craig M. (2003-02-17). "Oxidative degradation of benzene rings". Tetrahedron. 59 (8): 1105–1136. doi:10.1016/S0040-4020(02)01492-8. ISSN 0040-4020.
  14. ^ Mashiko, K.; Miyamoto, T. (1998). "Latent Fingerprint Processing by the Ruthenium Tetroxide Method". Journal of Forensic Identification. 48 (3): 279–290. doi:10.3408/jasti.2.21.
  15. ^ Ronneau, C.; Cara, J.; Rimski-Korsakov, A. (1995). "Oxidation-enhanced emission of ruthenium from nuclear fuel". Journal of Environmental Radioactivity. 26: 63–70. doi:10.1016/0265-931X(95)91633-F.
  16. ^ Beuzet, Emilie; Lamy, Jean-Sylvestre; Perron, Hadrien; Simoni, Eric; Ducros, Gérard (2012). "Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code". Nuclear Engineering and Design. 246: 157–162. doi:10.1016/j.nucengdes.2011.08.025.

Further reading edit

  • Cotton, S.A. (1997). Chemistry of Precious Metals. London: Chapman and Hall. ISBN 978-0-7514-0413-5.
  • Farmer, V.; Welton, T. (2002). "The oxidation of alcohols in substituted imidazolium ionic liquids using ruthenium catalysts". Green Chemistry. 4 (2): 97. doi:10.1039/B109851A.
  • Singh, B.; Srivastava, S. (1991). "Kinetics and mechanism of ruthenium tetroxide catalysed oxidation of cyclic alcohols by bromate in a base". Transition Metal Chemistry. 16 (4): 466. doi:10.1007/BF01129466. S2CID 95711945.
  • Courtney, J.L.; Swansbor, K.F. (1972). "Ruthenium tetroxide oxidation". Reviews of Pure and Applied Chemistry. 22: 47.

January 01, 1970
ruthenium, tetroxide, inorganic, compound, with, formula, ruo4, yellow, volatile, solid, that, melts, near, room, temperature, odor, ozone, samples, typically, black, impurities, analogous, oso4, more, widely, used, better, known, also, anhydride, hyperrutheni. Ruthenium tetroxide is the inorganic compound with the formula RuO4 It is a yellow volatile solid that melts near room temperature 2 It has the odor of ozone 3 Samples are typically black due to impurities The analogous OsO4 is more widely used and better known It is also the anhydride of hyperruthenic acid H2RuO5 One of the few solvents in which RuO4 forms stable solutions is CCl4 4 Ruthenium VIII oxide Names IUPAC name Ruthenium VIII oxide Identifiers CAS Number 20427 56 9 Y 3D model JSmol Interactive image ChemSpider 106401 ECHA InfoCard 100 039 815 EC Number 243 813 8 PubChem CID 119079 UNII 97E960G9RP Y CompTox Dashboard EPA DTXSID20174373 InChI InChI 1S 4O RuKey GJFMDWMEOCWXGJ UHFFFAOYSA N SMILES O Ru O O O Properties Chemical formula RuO4 Molar mass 165 07 g mol Appearance yellow easily melting solid Odor pungent Density 3 29 g cm3 Boiling point 129 6 1 C 265 3 F 402 8 K Solubility in water 2 w v at 20 C Solubility in other solvents Soluble inCarbon tetrachlorideChloroform Structure Molecular shape tetrahedral Dipole moment zero Hazards NFPA 704 fire diamond 301 Safety data sheet SDS external MSDS sheet Related compounds Related compounds Ruthenium dioxide Ruthenium trichloride Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Contents 1 Preparation 2 Structure 3 Uses 3 1 Isolation of ruthenium from ores 3 2 Organic chemistry 3 3 Other uses 4 Gaseous release by nuclear accidents 5 References 6 Further readingPreparation editRuO4 is prepared by oxidation of ruthenium III chloride with NaIO4 2 The reaction initially produces sodium diperiodo dihydroxo ruthenate VI which then decomposes in acid solution to the tetroxide 5 8 Ru3 aq 5 IO4 aq 12 H2O l 8 RuO4 s 5 I aq 24 H aq 6 Due to its challenging reactivity RuO4 it is always generated in situ and used in catalytic quantities at least in organic reactions 4 Structure editRuO4 forms two crystal structures one with cubic symmetry and another with monoclinic symmetry isotypic to OsO4 The molecule adopts a tetrahedral geometry with the Ru O distances ranging from 169 to 170 pm 7 Uses editIsolation of ruthenium from ores edit The main commercial value of RuO4 is as an intermediate in the production of ruthenium compounds and metal from ores Like other platinum group metals PGMs ruthenium occurs at low concentrations and often mixed with other PGMs Together with OsO4 it is separated from other PGMs by distillation of a chlorine oxidized extract Ruthenium is separated from OsO4 by reducing RuO4 with hydrochloric acid a process that exploits the highly positive reduction potential for the RuO4 0 couple 8 9 Organic chemistry edit This section does not cite any sources Please help improve this section by adding citations to reliable sources Unsourced material may be challenged and removed October 2022 Learn how and when to remove this message RuO4 is of specialized value in organic chemistry because it oxidizes virtually any hydrocarbon For example it will oxidize adamantane to 1 adamantanol Because it is such an aggressive oxidant reaction conditions must be mild generally room temperature Although a strong oxidant RuO4 oxidations do not perturb stereocenters that are not oxidized Illustrative is the oxidation of the following diol to a carboxylic acid nbsp Oxidation of epoxy alcohols also occurs without degradation of the epoxide ring nbsp Under milder conditions oxidative reaction yields aldehydes instead RuO4 readily converts secondary alcohols into ketones Although similar results can be achieved with other cheaper oxidants such as PCC or DMSO based oxidants RuO4 is ideal when a very vigorous oxidant is needed but mild conditions must be maintained It is used in organic synthesis to oxidize internal alkynes to 1 2 diketones and terminal alkynes along with primary alcohols to carboxylic acids When used in this fashion the ruthenium VIII oxide is used in catalytic amounts and regenerated by the addition of sodium periodate to ruthenium III chloride and a solvent mixture of acetonitrile water and carbon tetrachloride RuO4 readily cleaves double bonds to yield carbonyl products in a manner similar to ozonolysis OsO4 a more familiar oxidant that is structurally similar to RuO4 does not cleave double bonds instead producing vicinal diol products However with short reaction times and carefully controlled conditions RuO4 can also be used for dihydroxylation 10 Because RuO4 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 RuO4 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 11 12 13 nbsp Although used as a direct oxidant due to the relatively high cost of RuO4 it is also used catalytically with a cooxidant For an oxidation of cyclic alcohols with RuO4 as a catalyst and bromate as oxidant under basic conditions RuO4 is first activated by hydroxide turning into the hyperruthenate anion RuO4 OH HRuO5 The reaction proceeds via a glycolate complex Other uses edit 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 14 Gaseous release by nuclear accidents editBecause of the very high volatility of ruthenium tetroxide RuO4 ruthenium radioactive isotopes with their relative short half life are considered as the second most hazardous gaseous isotopes after iodine 131 in case of release by a nuclear accident 15 3 16 The two most important radioactive isotopes of ruthenium are 103Ru and 106Ru They have half lives of 39 6 days and 373 6 days respectively 3 References edit Koda Yoshio 1986 Boiling Points and Ideal Solutions of Ruthenium and Osmium Tetraoxides Journal of the Chemical Society Chemical Communications 1986 17 1347 1348 doi 10 1039 C39860001347 a b H L Grube 1963 Ruthenium VIII Oxide In G Brauer ed Handbook of Preparative Inorganic Chemistry 2nd Ed Vol 1 NY Academic Press pp 1599 1600 a b c Backman U Lipponen M Auvinen A Jokiniemi J amp Zilliacus R 2004 Ruthenium behaviour in severe nuclear accident conditions Final report No NKS 100 Nordisk Kernesikkerhedsforskning a b Martin V S Palazon J M Rodriguez C M Nevill C R 2006 Ruthenium VIII Oxide Encyclopedia of Reagents for Organic Synthesis doi 10 1002 047084289X rr009 pub2 ISBN 978 0471936237 Mercer E E Meyer S M 1972 1 July 1971 A periodate complex of ruthenium VI J Inorg Nucl Chem 34 2 Great Britain Pergamon 777 778 doi 10 1016 0022 1902 72 80466 4 Carlsen Per H J Katsuki Tsutomu Martin Victor S Sharpless K Barry September 1981 A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds The Journal of Organic Chemistry 46 19 3936 3938 doi 10 1021 jo00332a045 ISSN 0022 3263 Pley M Wickleder M S 2005 Two Crystalline Modifications of RuO4 Journal of Solid State Chemistry 178 10 3206 3209 Bibcode 2005JSSCh 178 3206P doi 10 1016 j jssc 2005 07 021 Bernardis Francesco L Grant Richard A Sherrington David C 2005 A review of methods of separation of the platinum group metals through their chloro complexes Reactive and Functional Polymers 65 3 205 217 doi 10 1016 j reactfunctpolym 2005 05 011 Swain P Mallika C Srinivasan R Mudali U K Natarajan R 2013 Separation and recovery of ruthenium a review Journal of Radioanalytical and Nuclear Chemistry 298 2 781 796 doi 10 1007 s10967 013 2536 5 S2CID 95804621 Plietker Bernd 2005 Selectivity versus reactivity recent advances in RuO4 catalyzed oxidations Synthesis 5 15 2453 2472 doi 10 1055 s 2005 872172 Nunez M Teresa Martin Victor S March 1990 Efficient oxidation of phenyl groups to carboxylic acids with ruthenium tetraoxide A simple synthesis of R gamma caprolactone the pheromone of Trogoderma granarium The Journal of Organic Chemistry 55 6 1928 1932 doi 10 1021 jo00293a044 ISSN 0022 3263 Nasr Khaled Pannier Nadine Frangioni John V Maison Wolfgang February 2008 Rigid Multivalent Scaffolds Based on Adamantane The Journal of Organic Chemistry 73 3 1056 1060 doi 10 1021 jo702310g ISSN 0022 3263 PMC 2505186 PMID 18179237 Mander Lewis N Williams Craig M 2003 02 17 Oxidative degradation of benzene rings Tetrahedron 59 8 1105 1136 doi 10 1016 S0040 4020 02 01492 8 ISSN 0040 4020 Mashiko K Miyamoto T 1998 Latent Fingerprint Processing by the Ruthenium Tetroxide Method Journal of Forensic Identification 48 3 279 290 doi 10 3408 jasti 2 21 Ronneau C Cara J Rimski Korsakov A 1995 Oxidation enhanced emission of ruthenium from nuclear fuel Journal of Environmental Radioactivity 26 63 70 doi 10 1016 0265 931X 95 91633 F Beuzet Emilie Lamy Jean Sylvestre Perron Hadrien Simoni Eric Ducros Gerard 2012 Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code Nuclear Engineering and Design 246 157 162 doi 10 1016 j nucengdes 2011 08 025 Further reading editCotton S A 1997 Chemistry of Precious Metals London Chapman and Hall ISBN 978 0 7514 0413 5 Farmer V Welton T 2002 The oxidation of alcohols in substituted imidazolium ionic liquids using ruthenium catalysts Green Chemistry 4 2 97 doi 10 1039 B109851A Singh B Srivastava S 1991 Kinetics and mechanism of ruthenium tetroxide catalysed oxidation of cyclic alcohols by bromate in a base Transition Metal Chemistry 16 4 466 doi 10 1007 BF01129466 S2CID 95711945 Courtney J L Swansbor K F 1972 Ruthenium tetroxide oxidation Reviews of Pure and Applied Chemistry 22 47 Retrieved from https en wikipedia org w index php title Ruthenium tetroxide amp oldid 1217573266, wikipedia, wiki, book, books, library,

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