Chemistry Tutorial: Aromaticity

Based on a Chemistry 14C Honors Project

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(a) Befine each teim
(b) Explain how it ielates to aiomaticity
- Aiomaticity
- Conjugation
- Cyclic uelocalization
- Resonance
- Pi bonus
- Paitial Pi bonus
- Ring Stiain

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FG&2G*&H,
Aiomaticity is special stability pioviueu to a molecule upon possessing foui specific
qualities mentioneu below. To ueteimine if a molecule is aiomatic, investigate its stiuctuie
foi the qualifieis. If all aie piesent within the molecule, then it is aiomatic.

"2*%&2*. I#2 82#6.%*)*%3,
- Pi bonus must lie within cyclic stiuctuie
- Each atom in the cycle must have 1 oibital, foiming 1 oibital loop
- All 1 oibitals in the loop must oveilap (planaiity)
- Bckel's Rule: oibital aiiangement must iesult in a loweiing of eneigy. 4n + 2 pi
elections (n is an integei: u, 1, 2, S, etc.) in the loop

DJ.6K1& L2#/1&6,
Beteimine if the following molecule is aiomatic.





Step 1: Bo pi bonus lie within a cyclic stiuctuie.

- Thiee pi bonus aie piesent, each lying within
the cyclic stiuctuie of benzene


! Yes


Step 2: Boes each atom in the cycle have a 1 oibital, foiming a 1 oibital loop.

- Each atom has a 1 oibital, foiming a loop


! Yes


Step S: Bo all 1 oibitals oveilap anu lie within the same plane.


- By iotating the molecule, we see that all
oibitals lie within the same plane


! Yes




Step 4: Boes the molecule follow Bckel's Rule.

6 total pi elections
4n + 2 = 6 n = 1

! Yes

C#8(04.'#87 K28H282 '. %8 %"#$%&'( $#02(402


L2.)%*)& L2#/1&6',
Beteimine whethei oi not the following molecules aie aiomatic.




L2.)%*)& L2#/1&6', (#10%*#$'

RA S2.I $22&. %00 ("'&2"'%

TA U#I 3#2. 8#& '8(0432 0##1 #6 #;2"0%11'8E 1 #"/'&%0.

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WA S2.I $22&. %00 ("'&2"'%

XA U#I 3#2. 8#& 6#00#9 <=(>20?. @402

YA S2.I $22&. %00 ("'&2"'%




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FG&2G*&H,
Conjugation iequiies at least thiee oveilapping 1 oibitals in the same plane so that
elections can be uelocalizeu foi bettei stability. Aiomaticity cannot exist without
conjugation because aiomatic molecules iequiie planaiity anu oveilapping 1 oibitals.
Bowevei, conjugation can exist in a molecule without being aiomatic.

DJ.6K1& L2#/1&6,
Beteimine if the molecule below has conjugation, aiomaticity, both, oi neithei.







Step 1: Boes the molecule have conjugation.


! Yes, the atoms aie all planai with moie than
thiee oveilapping 1 oibitals



Step 2: Is the molecule aiomatic.


! Pi bonus aie piesent within a cyclic stiuctuie





! Each atom has a 1 oibital, foiming a loop
! P oibitals oveilap anu lie in the same plane



" violates Bckel's Rule (4n+2 = 8; n = 64)

" Not aiomatic

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L2.)%*)& L2#/1&6', M "#$:07.%*#$ .$; 82#6.%*)*%3,
Beteimine if the molecules below have conjugation, aiomaticity, both, oi neithei.

1.

2.

S.


4.

S.
N
H

6.



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FG&2G*&H,
Resonance exists as a iesult of election uelocalization in a molecule. Biffeient
patteins emeige as a iesult of stiuctuie anu atom aiiangement within a molecule.
Resonance pioviues an extia stability uue to election uelocalization, anu consequently;
aiomatic iings have iesonance stiuctuies uue to cycling uouble bonus. Aiomatic
molecules must have iesonance; howevei, not all molecules with iesonant stiuctuies aie
aiomatic.

DJ.6K1& L2#/1&6,
Beteimine if the molecule below has iesonance, aiomaticity, both, oi neithei.






Step 1: Boes the molecule have iesonance.




- The pi bonus in the molecule can switch places, a piopeity seen in alkene
iings, iesulting in a iesonance hybiiu:






! Bas Resonance

Step 2: Is the molecule aiomatic.

! Yes, the atoms aie all planai with moie than
thiee oveilapping 1 oibitals
! Pi bonus aie piesent within a cyclic stiuctuie
! Each atom has a 1 oibital, foiming a loop
! The 1 oibitals oveilap anu lie in same plane

! Satisfies Bckel's Rule (4n+2 = 14; n = S)
! Aiomatic


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L2.)%*)& L2#/1&6', =&'#$.$)& .$; 82#6.%*)*%3
Beteimine if the molecules below have iesonance, aiomaticity, both, oi neithei.

1
O

2

S


4 CB
S
CB
2
CB
2
NB
2
S

6
S



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M 82& )#$:07.%*#$ .$; .2#6.%*)*%3 %N& '.6& %N*$7O
o Not quite. Conjugation occuis in aiomatic molecules, but aiomaticity is a highei
level of stability with moie iequiiements to be met. Conjugation can be vieweu
as simply a piece of aiomaticity.
- PN3 H#01; . 6#1&)01& K2&I&2 %# /& .2#6.%*)O
o Equilibiium favois stability. Aiomatic molecules have a special "extia" stability
causeu by the natuie of theii stiuctuie, anu aie haiuei to bieak apait.
- Q#H ).$ R %&11 *I . 6#1&)01& H*%N S*%2#7&$ *' .2#6.%*)O
o It uepenus on the molecule. If nitiogen is pait of a iing, check its hybiiuization
anu elections. If it is .1
2
hybiiuizeu oi if it can become .1
2
hybiiuizeu as a iesult
of the oveiall stiuctuie anu election uelocalization of the molecule, the molecule
is aiomatic.
- PN.% ;# 1#$& K.*2' N.G& %# ;# H*%N .2#6.%*)*%3O
o Lone paiis can leau to iesonance hybiius oi iesiue in pi bonus that contiibute to
the aiomaticity of a molecule.
- ".$ K02&13 1*$&.2 6#1&)01&' N.G& .2#6.%*)*%3O
o No. A iequiiement foi aiomaticity is a closeu loop oi iing oi 1 oibitals. Since
lineai molecules cannot achieve this, they aie unable to be classifieu as aiomatic.
- RI . 6#1&)01& )#$%.*$' .$ .2#6.%*) 2*$7T '0)N .' . /&$U&$& 2*$7T .%%.)N&; %# . $#$M
.2#6.%*) 2*$7T N#H ;#&' %N.% .II&)% %N& #G&2.11 .2#6.%*)*%3 #I %N& 6#1&)01&O
o 0veiall, a molecule can fail to meet the qualifications foi aiomaticity as a whole,
but still contain aiomatic paits. If a molecule contains a benzene iing, we can
say that the molecule has an aiomatic iing, but we cannot say that the molecule
is aiomatic.



o Example: Within the above molecules, theie aie aiomatic paits, outlineu in ieu.
Bowevei, the molecules as a whole aie not aiomatic.
- PN.% ;#&' %N& $ #I QV)A&1W' =01& 2&K2&'&$%T .$; HN.% ;#&' *% 6&.$ *I *% *' .$
*$%&7&2 #2 $#% .$ *$%&7&2O
o The "n" of Bckel's Rule is simply an inuicatoi of aiomaticity. It uoes not "stanu
foi" a ceitain woiu, but is insteau useu as a calculatoi. If "n" is a whole numbei
integei, the molecule can be aiomatic, anu if "n" is a fiaction oi non-integei, the
molecule is not aiomatic.
- Q#H ).$ R %&11 *I . 6#1&)01& N.' K1.$.2*%3O
o The best way is to builu a mouel. Remembei that to have a planai loop of 1
oibitals, the molecule must have at least thiee 'points' of inteiest, atoms oi 1
oibitals, in oiuei to foim a plane. Aftei you have ueteimineu this, check to see if
the atoms have 1 oibitals, anu that they aie aujacent.
- 5#&' .$ .2#6.%*) 6#1&)01& $&&; %# N.G& )#$:07.%*#$ .$; 2&'#$.$)&O
o Aiomatic molecules must have conjugation, anu geneially, because they contain
a seiies of 1 oibitals anu pi bonus, iesonance occuis. An aiomatic molecule
always has conjugation anu iesonance, but not all molecules that have
conjugation anuoi iesonance aie also aiomatic.
- Q#H ;# R )#0$% %N& K* &1&)%2#$' %# K107 *$%# %N& &@0.%*#$ #I QV)A&1W' =01&O
o Bckel's Rule (4n + 2 = # pi elections) applies only to the pi elections piesent in
the closeu loop of 1 oibitals. Finu the 1 oibitals piesent in molecule anu
ueteimine the numbei of elections in each. Sometimes, this is veiy appaient, as
uouble bonus imply two pi elections. Be caieful, though, as oxygen anu nitiogen
atoms can sometimes have an 'empty' 1 oibital, oi elections can be foiceu into a
1 oibital to achieve conjugation anu aiomaticity.
(&)%*#$ C, "#66#$ D22#2'

82#6.%*)*%3 #I ?02.$ .$; L322#1&

O

N
H


Fuian Pyiiole

Fuian anu pyiiole aie both aiomatic molecules. At fiist sight, these molecules seem
to be non-planai without a closeu loop of 1 oibitals; howevei, because of the benefits of
achieving aiomaticity, the stiuctuie is such that two lone paii elections aie uelocalizeu,
shown below:


By looking at the iesonance hybiiu, we can see the
uelocalization of one lone paii of elections on the oxygen.




The othei election paii is locateu somewheie in the 1 oibital of
oxygen, which is now .1
2
hybiiuizeu.





The elections aie uelocalizeu
thioughout the planai iing,
cieating a clouu of pi elections.




In a final ueteiminant of aiomaticity, by counting the pi
elections, we see that fuian follows Bckel's iule.







"#0$%*$7 L* &1&)%2#$'

- PN.% *' . K* &1&)%2#$O

o A pi election is an election involveu in a pi bonu.

- PN.% *' . K* /#$;O

o A pi bonu is an oveilap of two aujacent 1 oibitals between two atoms.

- 5#0/1& X#$;',

o Consist of 1 sigma bonu anu 1 pi bonu.

o A pi bonu contains 2 pi elections.

o Theiefoie, when counting pi elections, you know that foi each uouble bonu,
theie aie two pi elections piesent.

- X& ".2&I01, ?02.$YL322#1&,

o Sometimes, iesonance will cause .1
S
atoms to become .1
2
hybiiuizeu.
Election uelocalization anu aiomaticity is achieveu by uelocalizing one lone
paii, which will count as two pi elections in the system foi the puipose of
Bckel's equation.
(&)%*#$ E, F%N&2 =&.;*$7' .$; DJ%2. (#02)&' %# "#$'01%


82#6.%*)*%3 *$ "N&6*'%23 +<" X##A',

Chemistiy 14C Thinkbook

Chemistiy 14C Lectuie Supplement

0iganic Chemistiy as a Seconu Language (Klein)

0iganic Chemistiy: Stiuctuie anu Function (vollhaiut anu Schoie) anu Stuuy uuiue



F$1*$& P&/'*%&'

"Aiomatic Compounus anu Aiomaticity." Bi Anuy Cammiuge's Bomepage. 0niveisity of
East Anglia. 24 Nov. 2uu8 <http:www.uea.ac.uk~c286aiomaticnotes.htm>.
This website gives gieat insights about the basics of aiomaticity, geneial
concepts, anu ielateu vocabulaiy. It also gives in-uepth views of aiomatic
compounus anu the quantum mechanics behinu theii election uelocalization.

"Aiomaticity anu Bckel's Rule." 0=CBem. 0niveisity of Southein Naine. 24 Nov. 2uu8
<http:web1.uct.usm.maine.euu~newtonChy2S1_2SSLectuiesAiomaticityAiomaticityFS.html>
This website talks about Bckel's iule. It specifically elaboiates about the
election placement in aiomatic iings anu compounus, ielating it back to
moleculai oibitals, bonuing, anu how hybiiuization woiks.

Wikipeuia. "Aiomaticity." Aiomaticity. 14 Nov. 2uu8. Wikipeuia: The Fiee Encyclopeuia. 24
Nov. 2uu8 <http:en.wikipeuia.oigwikiaiomaticity>.
Although this site uoes not go in uepth like the otheis, it pioviues useful
infoimation about the geneial topic of aiomaticity, the qualifications, anu
moleculai stiuctuie.

Wikipeuia. "Fuian." Fuian. 14 Nov. 2uu8. Wikipeuia: The Fiee Encyclopeuia. 24 Nov. 2uu8
<http:en.wikipeuia.oigwikifuian>.
This page specifically talks about why fuian achieves aiomaticity. It pioviues a
useful uiagiam of the iesonance stiuctuies anu election uelocalization leauing to
stability.