Osmium dioxide

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Osmium dioxide
Osmium(IV) oxide Rutile-unit-cell-3D-balls.png
Osmium(IV) oxide
Names
IUPAC name
Osmium dioxide
Other names
Osmium(IV) oxide
Identifiers
PubChem CID
Properties
OsO2
Molar mass 222.229 g/mol
Appearanceblack or yellow brown
Density 11.4 g/cm3
Melting point 500 °C (932 °F; 773 K) (decomposes)
Related compounds [1]
Related osmium oxides
Osmium tetroxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Osmium dioxide is an inorganic compound with the formula OsO2. It exists as brown to black crystalline powder, but single crystals are golden and exhibit metallic conductivity. The compound crystallizes in the rutile structural motif, i.e. the connectivity is very similar to that in the mineral rutile.

Contents

Preparation

OsO2 can be obtained by the reaction of osmium with a variety of oxidizing agents, including, sodium chlorate, osmium tetroxide, and nitric oxide at about 600 °C. [2] [3] Using chemical transport, one can obtain large crystals of OsO2, sized up to 7x5x3 mm3. Single crystals show metallic resistivity of ~15 μΩ cm. A typical transport agent is O
2
via the reversible formation of volatile OsO4: [4]

OsO2 + O2 OsO4

Reactions

OsO2 does not dissolve in water, but is attacked by dilute hydrochloric acid. [5] [6] The crystals have rutile structure. [7] Unlike osmium tetroxide, OsO2 is not toxic. [8]

Related Research Articles

<span class="mw-page-title-main">Osmium</span> Chemical element with atomic number 76 (Os)

Osmium is a chemical element; it has symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a trace element in alloys, mostly in platinum ores. Osmium is the densest naturally occurring element. When experimentally measured using X-ray crystallography, it has a density of 22.59 g/cm3. Manufacturers use its alloys with platinum, iridium, and other platinum-group metals to make fountain pen nib tipping, electrical contacts, and in other applications that require extreme durability and hardness.

<span class="mw-page-title-main">Ruthenium</span> Chemical element with atomic number 44 (Ru)

Ruthenium is a chemical element; it has symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is unreactive to most chemicals. Karl Ernst Claus, a Russian scientist of Baltic-German ancestry, discovered the element in 1844 at Kazan State University and named it in honor of Russia, using the Latin name Ruthenia. Ruthenium is usually found as a minor component of platinum ores; the annual production has risen from about 19 tonnes in 2009 to some 35.5 tonnes in 2017. Most ruthenium produced is used in wear-resistant electrical contacts and thick-film resistors. A minor application for ruthenium is in platinum alloys and as a chemical catalyst. A new application of ruthenium is as the capping layer for extreme ultraviolet photomasks. Ruthenium is generally found in ores with the other platinum group metals in the Ural Mountains and in North and South America. Small but commercially important quantities are also found in pentlandite extracted from Sudbury, Ontario, and in pyroxenite deposits in South Africa.

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

Osmium tetroxide (also osmium(VIII) oxide) is the chemical compound with the formula OsO4. The compound is noteworthy for its many uses, despite its toxicity and the rarity of osmium. It also has a number of unusual properties, one being that the solid is volatile. The compound is colourless, but most samples appear yellow. This is most likely due to the presence of the impurity OsO2, which is yellow-brown in colour. In biology, its property of binding to lipids has made it a widely-used stain in electron microscopy.

Ruthenium tetroxide is the inorganic compound with the formula RuO4. It is a yellow volatile solid that melts near room temperature. It has the odor of ozone. 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.

In chemistry, hypomanganate, also called manganate(V) or tetraoxidomanganate(3−), is a trivalent anion (negative ion) composed of manganese and oxygen, with formula MnO3−
4
.

<span class="mw-page-title-main">Ruthenium(IV) oxide</span> Chemical compound

Ruthenium(IV) oxide is the inorganic compound with the formula RuO2. This black solid is the most common oxide of ruthenium. It is widely used as an electrocatalyst for producing chlorine, chlorine oxides, and O2. Like many dioxides, RuO2 adopts the rutile structure.

<span class="mw-page-title-main">Tungsten(IV) oxide</span> Chemical compound

Tungsten(IV) oxide is the chemical compound with the formula WO2. The bronze-colored solid crystallizes in a monoclinic cell. The rutile-like structure features distorted octahedral WO6 centers with alternate short W–W bonds (248 pm). Each tungsten center has the d2 configuration, which gives the material a high electrical conductivity.

Osmium compounds are compounds containing the element osmium (Os). Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds Na
2
[Os
4
(CO)
13
]
and Na
2
[Os(CO)
4
]
are used in the synthesis of osmium cluster compounds.

Ruthenium compounds are compounds containing the element ruthenium (Ru). Ruthenium compounds can have oxidation states ranging from 0 to +8, and −2. The properties of ruthenium and osmium compounds are often similar. The +2, +3, and +4 states are the most common. The most prevalent precursor is ruthenium trichloride, a red solid that is poorly defined chemically but versatile synthetically.

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.

The Lemieux–Johnson or Malaprade–Lemieux–Johnson oxidation is a chemical reaction in which an olefin undergoes oxidative cleavage to form two aldehyde or ketone units. The reaction is named after its inventors, Raymond Urgel Lemieux and William Summer Johnson, who published it in 1956. The reaction proceeds in a two step manner, beginning with dihydroxylation of the alkene by osmium tetroxide, followed by a Malaprade reaction to cleave the diol using periodate. Periodate also serves to regenerate the osmium tetroxide. This means only a catalytic amount of the osmium reagent is needed and also that the two consecutive reactions can be performed as a single tandem reaction process. The Lemieux–Johnson reaction ceases at the aldehyde stage of oxidation and therefore produces the same results as ozonolysis.

<span class="mw-page-title-main">Rhenium(IV) oxide</span> Chemical compound

Rhenium(IV) oxide or rhenium dioxide is the inorganic compound with the formula ReO2. This gray to black crystalline solid is a laboratory reagent that can be used as a catalyst. It adopts the rutile structure.

<span class="mw-page-title-main">Osmium(IV) chloride</span> Chemical compound

Osmium(IV) chloride or osmium tetrachloride is the inorganic compound composed of osmium and chlorine with the empirical formula OsCl4. It exists in two polymorphs (crystalline forms). The compound is used to prepare other osmium complexes.

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

Potassium osmate is the inorganic compound with the formula K2[OsO2(OH)4]. This diamagnetic purple salt contains osmium in the VI (6+) oxidation state. When dissolved in water a red solution is formed. When dissolved in ethanol, the salt gives a pink solution, and it gives a blue solution when dissolved in methanol. The salt gained attention as a catalyst for the asymmetric dihydroxylation of olefins.

Osmium iodide refers to compounds of osmium with the formula OsIn. Several have been mentioned in the literature, but only the triiodide has been verified by X-ray crystallography.

Robert Day Shannon is a retired research chemist formerly at DuPont de Nemours, Inc.

<span class="mw-page-title-main">Terbium compounds</span> Chemical compounds with at least one terbium atom

Terbium compounds are compounds formed by the lanthanide metal terbium (Tb). Terbium generally exhibits the +3 oxidation state in these compounds, such as in TbCl3, Tb(NO3)3 and Tb(CH3COO)3. Compounds with terbium in the +4 oxidation state are also known, such as TbO2 and BaTbF6. Terbium can also form compounds in the 0, +1 and +2 oxidation states.

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.

Iridium compounds are compounds containing the element iridium (Ir). Iridium forms compounds in oxidation states between −3 and +9, but the most common oxidation states are +1, +2, +3, and +4. Well-characterized compounds containing iridium in the +6 oxidation state include IrF6 and the oxides Sr2MgIrO6 and Sr2CaIrO6. iridium(VIII) oxide was generated under matrix isolation conditions at 6 K in argon. The highest oxidation state (+9), which is also the highest recorded for any element, is found in gaseous [IrO4]+.

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

Hassium tetroxide (also hassium(VIII) oxide) is the inorganic compound with the formula HsO4. It is the highest oxide of hassium, a transactinide transition metal. It has little use outside of scientific interest, where it is often studied in comparison to osmium tetroxide and ruthenium tetroxide, its lighter octavalent group 8 element analogs.

References

  1. OsO2 at webelements
  2. A. F. Holleman & E. Wiberg (2001). Inorganic chemistry. Academic Press. p. 1465. ISBN   0-12-352651-5.
  3. Thiele G.; Woditsch P. (1969). "Neutronenbeugungsuntersuchungen am Osmium(IV)-oxid". Journal of the Less Common Metals. 17 (4): 459. doi:10.1016/0022-5088(69)90074-5.
  4. Rogers, D. B.; Butler, S. R.; Shannon, R. D. (1972). "Single Crystals of Transition-Metal Dioxides". Inorganic Syntheses. Vol. XIII. pp. 135–145. doi:10.1002/9780470132449.ch27. ISBN   9780470132449.
  5. J. E. Greedan; D. B. Willson; T. E. Haas (1968). "Metallic nature of osmium dioxide". Inorg. Chem. 7 (11): 2461–2463. doi:10.1021/ic50069a059.
  6. Yen, P (2004). "Growth and characterization of OsO
    2
    single crystals". Journal of Crystal Growth. 262 (1–4): 271. doi:10.1016/j.jcrysgro.2003.10.021.
  7. Boman C.E.; Danielsen, Jacob; Haaland, Arne; Jerslev, Bodil; Schäffer, Claus Erik; Sunde, Erling; Sørensen, Nils Andreas (1970). "Precision Determination of the Crystal Structure of Osmium Dioxide". Acta Chemica Scandinavica. 24: 123–128. doi: 10.3891/acta.chem.scand.24-0123 .
  8. Smith, I.C., B.L. Carson, and T.L. Ferguson (1974). "Osmium: An appraisal of environmental exposure". Env Health Perspect. 8. National Institute of Environmental Health Sciences: 201–213. doi:10.2307/3428200. JSTOR   3428200. PMC   1474945 . PMID   4470919.{{cite journal}}: CS1 maint: multiple names: authors list (link)