If a molecule is aromatic then, we also can use this :- the molecule is DIATROPIC and PLANAR If a molecule is anti-aromatic, we also

can use this:- the molecule is PARATROPIC (it may be planar or nonplanar)

Since aromatic cycloheptatrienyl cations C7Me7+ and C7Ph7+ are known, but their complexes with transition metal ions are not known, most probably due to their non-planar but boatshaped structures.

According to huckels rule tropone and tropolone must be anti-aromatic because they contain

8-electrons. BUT they are having aromatic character and the reason is- electronegative atom oxygen in this case pulls the pi-electron(of C=O) towards itself and produces tropylium cation type structure. That is why tropolone exhibits aromatic character and undergoes electrophilic substitution, and gives tropolone.

But Cyclopentadienone---would produce a cyclopentadienyl cation, a 4-electrons system-antiaromaticity.

1,3,5,7-tetramethylcyclooctatetraene dication has 6 electrons spread over eight carbon atoms and the molecule is diatropic and planar.

DIPOLAR AROMATIC RESONANCE STRUCTURES

Systems of 8-electrons

Cyclo-octa-tetra-ene *not planar *tub-shaped structure *since not planar, hence this is neither aromatic nor anti-aromatic (since both requires planar structures) *a non-aromatic compound

CYCLO-OCTA-DI-ENE-DI-YNE

*planar *4 extra pi-electrons due to two triple bonds are not invoved in conjugation so total 8electrons are involved. *planar + 8 e-s = anti-aromatic

Benzocycloheptatrienyl anion

Anti-aromatic

1, 4-Biphenylene quinone

Anti-aromatic

SYSTEMS of 10-electrons [10]-annulene Predictions NMR study Aromaticity (what NMR study say, whether Calculations they are aromatic or not) Non-aromatic Non-aromatic

Geometrically possible isomers are (all are non-planar)

Cis-trans-cis-cis-trans

Non-aromatic

Non-aromatic

All cis

Non-aromatic

AROMATIC

Mono trans

Since a regular decagon demands for an angle of 144, these three(above) examples do not provide this requisite anglebut the following example provides nearly to this requisite angle and the examples are

the bridges of CH2- , -O- and NH- forces system to attain the requisite angle as much as possible. These three examples are nearly planar and possess 10-electrons and this fulfill the Huckels rule requirement and these are aromatic. A small distortion from planarity does not prevent aromaticity and a wonderful example is 1,3bis(trichloroacetyl)homoazulene

3D view of this molecule is given as:-

SYSTEMS OF MORE THAN 10-electrons

A) Those systems, which have (4n+2) -electrons :1) [14]-annulene

*internal hydrogens try to destroy planarity of molecule as in decagon, but much lesser in degree.so almost planar (A small distortion from planarity does not prevent aromaticity). Therefore this is AROMATIC. *So, molecule is diatropic and internal hydrogens has =0.00, while peripheral has 7.6 (full evidence of diamagnetic ring current). * Other [14]-annulenes are :-

AROMATIC *undoubtedly planar

AROMATIC *Bridged NH- groups maintain planarity AROMATIC *Bridged CH2- groups maintain planarity AROMATIC *one triple bond provide planarity to molecule, but this extra 2 -electrons do not take part in conjugation AROMATIC *four triple bond provide almost planarity, but these extra 8-electrons do not take part in conjugation

This [14]-annulene is non-aromatic, because CH2CH2- group (right side of the molecule, pointing below) destroy planarity. 2) Di-anions of [16]-annulene (18-electrons)

B) Those systems, which have 4n-electrons :-

*[12]-annulene *at -170C, the conformational mobility is greatly reduced, and molecule becomes almost planar, now, planar+12-electrons (4n system)=antiaromatic. Evidence comes from NMR datas- inner protons resonates at 8while outer at 6..a clear cut paratropic behavior of ring currentand molecule proved to be anti-aromatic. *at and above -150C all protons are magnetically equivalent. *at and above -50C, interaction between internal hydrogens leads to nonplanarity and molecules becomes unstable and rearranges to

*large bromine atom resides inside the ring *large Br and two -- bonds lead to planarity *anti-aromatic/paratropic *bridged N maintain planarity *anti-aromatic/paratropic *two cross-links maintain planarity *anti-aromatic/paratropic

*bridged CH2- group maintain planarity *anti-aromatic/paratropic