Manganese(III) acetate

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Manganese triacetate
Mn3O(OAc)6.png
Manganese(III) acetate dihydrate CAS 19513-05-4.jpg
Names
IUPAC name
Manganese triacetate
Other names
Manganese triacetate dihydrate; Manganese(III) acetate dihydrate, Manganic acetate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.012.365 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 213-602-5
PubChem CID
  • InChI=1S/3C2H4O2.Mn/c3*1-2(3)4;/h3*1H3,(H,3,4);/q;;;+3/p-3 Yes check.svgY
    Key: AHSBSUVHXDIAEY-UHFFFAOYSA-K Yes check.svgY
  • InChI=1/3C2H4O2.Mn/c3*1-2(3)4;/h3*1H3,(H,3,4);/q;;;+3/p-3
    Key: AHSBSUVHXDIAEY-DFZHHIFOAL
  • [Mn+3].O=C([O-])C.[O-]C(=O)C.[O-]C(=O)C
  • coordination complex:O1[C-](C)O[Mn+3]6([O-2]23)([OH])(O[C-](C)O4)O[C-](C)O[Mn+3]24([OH])(O[C-](C)O5)O[C-](C)O[Mn+3]135([OH])O[C-](C)O6
Properties
C6H9MnO6•2H2O
Molar mass 268.13 g/mol (dihydrate)
AppearanceBrown powder
Density 1.049 g cm−3, liquid; 1.266 g cm−3, solid
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
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 ?)

Manganese(III) acetate describes a family of materials with the approximate formula Mn(O2CCH3)3. These materials are brown solids that are soluble in acetic acid and water. They are used in organic synthesis as oxidizing agents. [1]

Contents

Structure

Although manganese(III) triacetate has not been reported, salts of basic manganese(III) acetate are well characterized. Basic manganese acetate adopts the structure reminiscent of those of basic chromium acetate and basic iron acetate. The formula is [Mn3O(O2CCH3)6Ln]X where L is a ligand and X is an anion. The salt [Mn3O(O2CCH3)6]O2CCH3.HO2CCH3 has been confirmed by X-ray crystallography. [2]

Preparation

It is usually used as the dihydrate, although the anhydrous form is also used in some situations. The dihydrate is prepared by combining potassium permanganate and manganese(II) acetate in acetic acid. [3] Addition of acetic anhydride to the reaction produces the anhydrous form. [1] [2] It is also synthesized by electrochemical method starting from Mn(OAc)2. [4]

Use in organic synthesis

Manganese triacetate has been used as a one-electron oxidant. It can oxidize alkenes via addition of acetic acid to form lactones. [3]

Manganese acetate lactone generic.png

This process is thought to proceed via the formation of a •CH2CO2H radical intermediate, which then reacts with the alkene, followed by additional oxidation steps and finally ring closure. [1] When the alkene is not symmetric, the major product depends on the nature of the alkene, and is consistent with initial formation of the more stable radical (among the two carbons of the alkene) followed by ring closure onto the more stable conformation of the intermediate. [5]

When reacted with enones, the carbon on the other side of the carbonyl reacts rather than the alkene portion, leading to α'-acetoxy enones. [6] In this process, the carbon next to the carbonyl is oxidized by the manganese, followed by transfer of acetate from the manganese to it. [7] It can similarly oxidize β-ketoesters at the α carbon, and this intermediate can react with various other structures, including halides and alkenes (see: manganese-mediated coupling reactions). One extension of this idea is the cyclization of the ketoester portion of the molecule with an alkene elsewhere in the same structure. [8]


See also

Related Research Articles

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In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure, or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.

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

A permanganate is a chemical compound containing the manganate(VII) ion, MnO
4
, the conjugate base of permanganic acid. Because the manganese atom is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion is a transition metal oxo complex with tetrahedral geometry. Permanganate solutions are purple in color and are stable in neutral or slightly alkaline media. The exact chemical reaction is dependent upon the organic contaminants present and the oxidant utilized. For example, trichloroethane (C2H3Cl3) is oxidized by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

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Rhodium(II) acetate is the coordination compound with the formula Rh2(AcO)4, where AcO is the acetate ion (CH
3
CO
2
). This dark green powder is slightly soluble in polar solvents, including water. It is used as a catalyst for cyclopropanation of alkenes. It is a widely studied example of a transition metal carboxylate complex.

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<span class="mw-page-title-main">Manganese(II) acetate</span> Chemical compound

Manganese(II) acetate are chemical compounds with the formula Mn(CH3CO2)2·(H2O)n where n = 0, 2, 4. These materials are white or pale pink solids. Some of these compounds are used as a catalyst and as fertilizer.

Manganese-mediated coupling reactions are radical coupling reactions between enolizable carbonyl compounds and unsaturated compounds initiated by a manganese(III) salt, typically manganese(III) acetate. Copper(II) acetate is sometimes used as a co-oxidant to assist in the oxidation of intermediate radicals to carbocations.

Aluminium triacetate, formally named aluminium acetate, is a chemical compound with composition Al(CH
3
CO
2
)
3
. Under standard conditions it appears as a white, water-soluble solid that decomposes on heating at around 200 °C. The triacetate hydrolyses to a mixture of basic hydroxide / acetate salts, and multiple species co-exist in chemical equilibrium, particularly in aqueous solutions of the acetate ion; the name aluminium acetate is commonly used for this mixed system.

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α,β-Unsaturated carbonyl compound Functional group of organic compounds

α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals. In these compounds the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.

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Manganese(III) chloride is the hypothetical inorganic compound with the formula MnCl3.

References

  1. 1 2 3 Snider, Barry B. (2001). "Manganese(III) Acetate". Encyclopedia of Reagents for Organic Synthesis . Wiley. doi:10.1002/047084289X.rm018. ISBN   0471936235.
  2. 1 2 Hessel, L. W.; Romers, C. (1969). "The Crystal Structure of "Anhydrous Manganic Acetate"". Recueil des Travaux Chimiques des Pays-Bas. 88 (5): 545–552. doi:10.1002/recl.19690880505.
  3. 1 2 E. I. Heiba, R. M. Dessau, A. L. Williams, P. G. Rodewald (1983). "Substituted γ-butyrolactones From Carboxylic Acids And Olefins: γ-(n-octyl)-γ-butyrolactone". Org. Synth. 61: 22. doi:10.15227/orgsyn.061.0022.{{cite journal}}: CS1 maint: uses authors parameter (link)
  4. Yılmaz, M.; Yılmaz, E. V. B.; Pekel, A. T. (2011). "Radical Cyclization of Fluorinated 1,3-Dicarbonyl Compounds with Dienes Using Manganese(III) Acetate and Synthesis of Fluoroacylated 4,5-Dihydrofurans". Helv. Chim. Acta. 94 (11): 2027–2038. doi:10.1002/hlca.201100105.
  5. Fristad, W. E.; Peterson, J. R. (1985). "Manganese(III)-mediated γ-lactone annulation". J. Org. Chem. 50 (1): 10–18. doi:10.1021/jo00201a003.
  6. Dunlap, Norma K.; Sabol, Mark R.; Watt, David S. (1984). "Oxidation of enones to α'-acetoxyenones using manganese triacetate". Tetrahedron Letters. 25: 5839–5842. doi:10.1016/S0040-4039(01)81699-3.
  7. Williams, G. J.; Hunter, N. R. (1976). "Situselective α'-acetoxylationof some α,β-enones by manganic acetate oxidation". Can. J. Chem. 54 (24): 3830–3832. doi:10.1139/v76-550.
  8. Snider, B. B.; Patricia, J. J.; Kates, S. A. (1988). "Mechanism of manganese(III)-based oxidation of β-keto esters". J. Org. Chem. 53 (10): 2137–2141. doi:10.1021/jo00245a001.