Chromium(VI) oxide peroxide

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Chromium(VI) oxide peroxide
CrO5L.svg
Names
IUPAC name
Chromium(VI) oxide diperoxide
Other names
  • Chromium(VI) oxide peroxide
  • Chromium pentoxide
. chromium oxide peroxide, chromium(VI) oxide diperoxide
Identifiers
  • 35262-77-2 applies to "CrO5", which exists only as adducts, see image Yes check.svgY
3D model (JSmol)
ChEBI
ChemSpider
101104
PubChem CID
  • InChI=1/Cr.5O/q;;;-2;2*-1/rCrO4.O/c2-1(3,4)5;/q2*-2
    Key: ZWPVWTIRZYDPKW-NIUFNKCUAY
  • O0O[Cr]01(=O)OO1
Properties
CrO(O2)2
Molar mass 131.991 g·mol−1
AppearanceDark blue
soluble (decomposes)
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
May suddenly explode if unstabilized/dry, toxic and create highly carcinogenic chromium fumes.
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Chromium(VI) oxide peroxide is the name given to a collection of chromium coordination complexes. They have the formula CrO(O2)2L where L is a ligand. These species are dark blue and often labile. They all feature oxo ligand and two peroxo ligands, with the remaining coordination sites occupied by water, hydroxide, ether, or other Lewis bases. [1]

Contents

Preparation and properties

Structure of
CrO(O2)2(pyridine). Hydrogen atoms bonded to carbon atoms are omitted. Color code: Cr = gray, C= black, H = white, O= red, N = blue. PyCrO5-from-xtal-1964-CM-3D-balls.png
Structure of CrO(O2)2(pyridine). Hydrogen atoms bonded to carbon atoms are omitted. Color code: Cr = gray, C= black, H = white, O= red, N = blue.

Chromium(VI) oxide peroxide is formed by the addition of acidified hydrogen peroxide solutions to solutions of metal chromates or dichromates, such as sodium chromate or potassium dichromate. The generally yellow chromates or orange dichromates turn to dark blue as "chromium(VI) oxide peroxide" forms:

CrO2−4 + 2 H2O2 + H+[CrO(O2)2OH] + 3 H2O

The structure of the pyridine complex has been determined crystallographically. [2] Adducts with other N-heterocycles have also been characterized similarly. [3]

Aqueous chromium(VI) oxide peroxide decomposes in a few seconds, turning green as chromium(III) compounds are formed. [4]

2 CrO(O2)2 + 7 H2O2 + 6 H+ → 2 Cr3+ + 10 H2O + 7 O2

Stable adducts of the type CrO(O2)2L include those with L = diethyl ether, 1-butanol, ethyl acetate, or amyl acetate. They form by adding a layer of the organic solvent above the chromate/dichromate solution and shaking during the addition of hydrogen peroxide.

The etherate, bis(pyridine) and pyridine complexes of this compound have been found to be effective oxidants in organic chemistry. [5]

CrO5 is sometimes said to have a "Butterfly-like" Structure due to its arrangement according to Valence Bond Theory.

"BUTTERFLY STRUCTURE" CrO5-2D.png
"BUTTERFLY STRUCTURE"

See also

Related Research Articles

<span class="mw-page-title-main">Chromium</span> Chemical element with atomic number 24 (Cr)

Chromium is a chemical element; it has symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal.

<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.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

Chromic acid is jargon for a solution formed by the addition of sulfuric acid to aqueous solutions of dichromate. It consists at least in part of chromium trioxide.

<span class="mw-page-title-main">Chromate and dichromate</span> Chromium(VI) anions

Chromate salts contain the chromate anion, CrO2−
4
. Dichromate salts contain the dichromate anion, Cr
2
O2−
7
. They are oxyanions of chromium in the +6 oxidation state and are moderately strong oxidizing agents. In an aqueous solution, chromate and dichromate ions can be interconvertible.

<span class="mw-page-title-main">Chromium trioxide</span> Chemical compound

Chromium trioxide is an inorganic compound with the formula CrO3. It is the acidic anhydride of chromic acid, and is sometimes marketed under the same name. This compound is a dark-purple solid under anhydrous conditions and bright orange when wet. The substance dissolves in water accompanied by hydrolysis. Millions of kilograms are produced annually, mainly for electroplating. Chromium trioxide is a powerful oxidiser, a mutagen, and a carcinogen.

<span class="mw-page-title-main">Telluric acid</span> Chemical compound (Te(OH)6)

Telluric acid, or more accurately orthotelluric acid, is a chemical compound with the formula Te(OH)6, often written as H6TeO6. It is a white crystalline solid made up of octahedral Te(OH)6 molecules which persist in aqueous solution. In the solid state, there are two forms, rhombohedral and monoclinic, and both contain octahedral Te(OH)6 molecules, containing one hexavalent tellurium (Te) atom in the +6 oxidation state, attached to six hydroxyl (–OH) groups, thus, it can be called tellurium(VI) hydroxide. Telluric acid is a weak acid which is dibasic, forming tellurate salts with strong bases and hydrogen tellurate salts with weaker bases or upon hydrolysis of tellurates in water. It is used as tellurium-source in the synthesis of oxidation catalysts.

Chromium oxide may refer to:

<span class="mw-page-title-main">Vanadium compounds</span>

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO2+ center.

<span class="mw-page-title-main">Chromium compounds</span> Chemical compounds containing chromium

Chromium compounds are compounds containing the element chromium (Cr). Chromium is a member of group 6 of the transition metals. The +3 and +6 states occur most commonly within chromium compounds, followed by +2; charges of +1, +4 and +5 for chromium are rare, but do nevertheless occasionally exist.

<span class="mw-page-title-main">Collins reagent</span> Chemical compound

Collins reagent is the complex of chromium(VI) oxide with pyridine in dichloromethane. This metal-pyridine complex, a red solid, is used to oxidize primary alcohols to the corresponding aldehydes and secondary alcohols to the corresponding ketones. This complex is a hygroscopic orange solid.

<span class="mw-page-title-main">Sodium chromate</span> Chemical compound

Sodium chromate is the inorganic compound with the formula Na2CrO4. It exists as a yellow hygroscopic solid, which can form tetra-, hexa-, and decahydrates. It is an intermediate in the extraction of chromium from its ores.

<span class="mw-page-title-main">Potassium tetraperoxochromate(V)</span> Chemical compound

Potassium peroxochromate, potassium tetraperoxochromate(V), or simply potassium perchromate, is an inorganic compound having the chemical formula K3[Cr(O2)4]. It is a red-brown paramagnetic solid. It is the potassium salt of tetraperoxochromate(V), one of the few examples of chromium in the +5 oxidation state and one of the rare examples of a complex stabilized only by peroxide ligands. This compound is used as a source of singlet oxygen.

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Alcohol oxidation is a collection of oxidation reactions in organic chemistry that convert alcohols to aldehydes, ketones, carboxylic acids, and esters. The reaction mainly applies to primary and secondary alcohols. Secondary alcohols form ketones, while primary alcohols form aldehydes or carboxylic acids.

Oxidation with chromium(VI) complexes involves the conversion of alcohols to carbonyl compounds or more highly oxidized products through the action of molecular chromium(VI) oxides and salts. The principal reagents are Collins reagent, PDC, and PCC. These reagents represent improvements over inorganic chromium(VI) reagents such as Jones reagent.

<span class="mw-page-title-main">Jones oxidation</span> Oxidation of alcohol

The Jones oxidation is an organic reaction for the oxidation of primary and secondary alcohols to carboxylic acids and ketones, respectively. It is named after its discoverer, Sir Ewart Jones. The reaction was an early method for the oxidation of alcohols. Its use has subsided because milder, more selective reagents have been developed, e.g. Collins reagent.

A chromate ester is a chemical structure that contains a chromium atom (symbol Cr) in a +6 oxidation state that is connected via an oxygen (O) linkage to a carbon (C) atom. The Cr itself is in its chromate form, with several oxygens attached, and the Cr–O–C attachment makes this chemical group structurally similar to other ester functional groups. They can be synthesized from various chromium(VI) metal compounds, such as CrO3, chromium chloride complexes, and aqueous chromate ions, and tend to react via redox reactions to liberate chromium(IV).

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

MoOPH, also known as oxodiperoxymolybdenum(pyridine)-(hexamethylphosphoric triamide), is a reagent used in organic synthesis. It contains a molybdenum(VI) center with multiple oxygen ligands, coordinated with pyridine and HMPA ligands, although the HMPA can be replaced by DMPU. It is an electrophilic source of oxygen that reacts with enolates and related structures, and thus can be used for alpha-hydroxylation of carbonyl-containing compounds. Other reagents used for alpha-hydroxylation via enol or enolate structures include Davis oxaziridine, oxygen, and various peroxyacids. This reagent was first utilized by Edwin Vedejs as an efficient alpha-hydroxylating agent in 1974 and an effective preparative procedure was later published in 1978.

<span class="mw-page-title-main">Metal peroxide</span> Metal-containing compounds with peroxide (O2) ions/groups

In chemistry, metal peroxides are metal-containing compounds with ionically- or covalently-bonded peroxide groups. This large family of compounds can be divided into ionic and covalent peroxide. The first class mostly contains the peroxides of the alkali and alkaline earth metals whereas the covalent peroxides are represented by such compounds as hydrogen peroxide and peroxymonosulfuric acid. In contrast to the purely ionic character of alkali metal peroxides, peroxides of transition metals have a more covalent character.

References

  1. Gili, Pedro; Mederos, Alfredo; Lorenzo-Luis, Pablo A.; de la Rosa, Eduardo Medina; Muñoz, Alfonso (2002). "On the interaction of compounds of chromium(VI) with hydrogen peroxide. A study of chromium(VI) and (V) peroxides in the acid–basic pH range". Inorganica Chimica Acta. 331: 16–24. doi:10.1016/S0020-1693(01)00747-2.
  2. Stomberg, Rolf (1962). "Crystal Structure of Peroxochromates, CrO5⋅C5H5N". Nature . 196 (4854): 570–571. doi:10.1038/196570b0. S2CID   4187294.
  3. Stomberg, Rolf; Ainalem, Ing-Britt; Johansson, Gunnar; Tolboe, O.; Paasivirta, Jaakko (1968). "The Crystal Structure of two Modifications of Oxidodiperoxido-2,2'-dipyridylchromium(VI), [CrO(O2)2(C10H8N2)]". Acta Chemica Scandinavica. 22: 1439–1451. doi:10.3891/acta.chem.scand.22-1439.
  4. Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils; (1985). "Chromium" (in German). Lehrbuch der Anorganischen Chemie (91–100 ed.). Walter de Gruyter. pp. 1081–1095. ISBN   3-11-007511-3."
  5. Firouzabadi, H.; Iranpoor, N.; Kiaeezadeh, F.; Toofan, J. (1986). "Chromium(VI) based oxidants-1 Chromium peroxide complexes as versatile, mild, and efficient oxidants in organic synthesis". Tetrahedron . 42: 719. doi:10.1016/S0040-4020(01)87476-7.