Arenium ion

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Ball-and-stick model of the benzenium ion

An arenium ion in organic chemistry is a cyclohexadienyl cation that appears as a reactive

intermediate in electrophilic aromatic substitution.[1] For historic reasons this complex is also called
a Wheland intermediate[2] or a sigma complex or -complex. The smallest arenium ion
is benzenium ion C6H7+, which is protonated benzene.

Two hydrogen atoms bonded to one carbon lie in a plane perpendicular to the benzene ring.
[3]
The arenium ion is no longer an aromatic species; however it is relatively stable due to
delocalization: the positive charge is delocalized over 3 carbon atoms via the pi system, as
depicted on the following resonance structures:

A complexed electrophile can contribute to the stability of arenium ions.

A benzenium ion can be isolated as a stable compound when benzene is protonated by
the carborane superacid H(CB11H(CH3)5Br6).[4] The benzenium salt is crystalline with thermal
stability up to 150 C. Bond lengths deduced from X-ray crystallography are consistent with
a cyclohexadienyl cation structure.
In one study a methylene arenium ion is stabilized by metal complexation: [5]

In this reaction sequence the R-Pd(II)-Br starting complex 1 stabilized by TMEDA is

converted by dppe to metal complex 2. Electrophilic attack of methyl triflateforms
methylene arenium ion 3 with (based on X-ray crystallography) positive charge located
in aromatic para position and with the methylene group 6 out of the plane of the ring.
Reaction first with water and then with triethylamine hydrolyzes the ether group.

See also[edit]

List of publications in chemistry: Jerry March Advanced Organic Chemistry

Aryl radical

References[edit]
1.

Jump up^ Stable carbocations. CXVIII. General concept and structure of carbocations based on
differentiation of trivalent (classical) carbenium ions from three-center bound penta- of
tetracoordinated (nonclassical) carbonium ions. Role of carbocations in electrophilic
reactions George A. Olah J. Am. Chem. Soc.; 1972; 94(3) pp 808 - 820;doi:10.1021/ja00758a020

2.

Jump up^ A Quantum Mechanical Investigation of the Orientation of Substituents in Aromatic

Molecules G. W. Wheland J. Am. Chem. Soc.; 1942; 64(4) pp 900 - 908;doi:10.1021/ja01256a047

3.

Jump up^ A guidebook to mechanism in organic chemistry, Peter Sykes; pp 130-133

4.

Jump up^ Isolating Benzenium Ion Salts Christopher A. Reed, Kee-Chan Kim, Evgenii S.
Stoyanov, Daniel Stasko, Fook S. Tham, Leonard J. Mueller, and Peter D. W. Boyd J. Am. Chem.
Soc.; 2003; 125(7) pp 1796 - 1804; doi:10.1021/ja027336o

5.

Jump up^ Synthesis and Reactivity of the Methylene Arenium Form of a Benzyl Cation, Stabilized
by Complexation Elena Poverenov, Gregory Leitus, and David Milstein J. Am. Chem. Soc.; 2006;
128(51) pp 16450 - 16451; (Communication) doi:10.1021/ja067298z