Oxonium ion

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In chemistry, an oxonium ion is any oxygen cation with three bonds.[1] The simplest oxonium ion is the hydronium ion H3O+.[2]

Alkyloxonium[edit]

Hydronium is one of a series of oxonium ions with the formula R3−nHnO+. Oxygen is usually pyramidal with an sp3 hybridization. Those with n = 2 are called primary oxonium ions, an example being protonated methanol. Other hydrocarbon oxonium ions are formed by protonation or alkylation of alcohols or ethers (R−C−+O−R1R2). In acidic media, the oxonium functional group produced by protonating an alcohol can be a leaving group in the E2 elimination reaction. The product is an alkene. Extreme acidity, heat and dehydrating conditions are usually required.

Secondary oxonium ions have the formula R2OH+, an example being protonated ethers.

Tertiary have the formula R3O+, an example being trimethyloxonium.[3] Tertiary alkyloxonium salts are useful alkylating agents. For example, triethyloxonium tetrafluoroborate (Et
3
O+
)(BF
4
), a white crystalline solid, can be used, for example, to produce ethyl esters when the conditions of traditional Fischer esterification are unsuitable.[4] It is also used for preparation of enol ethers and related functional groups.[5][6]

Oxonium-ion-2D.png
Trimethyloxonium-2D-skeletal.png
Trimethyloxonium-3D-balls.png
Trimethyloxonium-3D-vdW.png
general pyramidal
oxonium ion
skeletal formula of the
trimethyloxonium cation
ball-and-stick model
of trimethyloxonium
space-filling model
of trimethyloxonium

Oxatriquinane and oxatriquinacene are unusually stable oxonium ions, first described in 2008. Oxatriquinane does not react with boiling water or with alcohols, thiols, halide ions, or amines, although it does react with stronger nucleophiles such as hydroxide, cyanide, and azide.

Oxocarbenium ions[edit]

Another class of oxonium ions encountered in organic chemistry is the oxocarbenium ions, obtained by protonation or alkylation of a carbonyl group e.g. R−C=+O−R′ which forms a resonance structure with the fully-fledged carbocation R−+C−O−R′ and is therefore especially stable:

Carbonyl-oxonium-resonance-2D-skeletal.png

See also[edit]

References[edit]

  1. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley, ISBN 0-471-85472-7 
  2. ^ George A. Olah (1998). Onium Ions. John Wiley & Sons. p. 509. ISBN 9780471148777. 
  3. ^ Olah, George A. (1993). "Superelectrophiles". Angew. Chem. Int. Ed. Engl. 32: 767–88. doi:10.1002/anie.199307673. 
  4. ^ Douglas J. Raber, Patrick Gariano, Jr, Albert O. Brod, Anne L. Gariano, And Wayne C. Guida "Esterification Of Carboxylic Acids With Trialkyloxonium Salts: Ethyl And Methyl 4-acetoxybenzoates" Org. Synth. 1977, 56, 59.doi:10.15227/orgsyn.056.0059
  5. ^ Justin R. Struble And Jeffrey W. Bode "Synthesis Of A N-mesityl Substituted Aminoindanol-derived Triazolium Salt" Org. Synth. 2010, 87, 362. doi:10.15227/orgsyn.087.0362
  6. ^ Lous S. Hegedus, Michael A. Mcguire, And Lisa M. Schultze "1,3-Dimethyl-3-methoxy-4-phenylazetidinone" Org. Synth. 1987, 65, 140.doi:10.15227/orgsyn.065.0140