1emplaLe 14b: AromauclLy

ChapLer 4 of 1exLbook
ChapLer 11 of L-LexLbook






















8enzene
llrsL dlscovered by Mlchael laraday ln 1823
by compressed lllumlnaung gas.
SLrucLure was noL deLermlned unul 1863 by kekule ln a
dream" (accordlng Lo mosL)
8easoned LhaL 8enzene does noL undergo alkene addluon
reacuons ls because of rapld lnLerconverslon beLween
slngle & double bonds.























1he Stab|||ty of 8enzene
8enzene ls Lhe besL and mosL famlllar example of a subsLance
LhaL possesses "_____________" or "____________"
Aromanc|ty -


Pow can we measure Lhls sLablllLy"?:



neat of hydrogenanon: compare experlmenLal value wlLh
"expecLed" value for hypoLheucal cyclohexaLrlene"
! "n
h
of benzne expected 3x(120 kI]mo|) = 360 kI]mo|






















Plgher ln Lnergy Lhan
8enzene!


"#$ %&'()*

"+, %&'()*

,"# %&'()*

+-# %&'()*
3 x cyclohexene
neats of
hydrogenanon:























"#$ %&'()*
+-# %&'()*


3 x cyclohexene
Cbserved heaL of
hydrogenauon ls 132 k!/
mol less Lhan "expecLed",
more sLable
132 k!/mol ls Lhe
resonance energy






















heaL of hydrogenauon = 208 k!/mol

heaL of hydrogenauon = 337 k!/mol

3P
2
L

3P
2
L

Cyc||c con[uganon versus
noncyc||c con[uganon






















Can we conclude LhaL all 8lngs LhaL
have alLernaung double and slngle
bonds llke benzene have Lhls exLra
sLablllzauon?






















Cyc|obutad|ene & Cyc|ooctatetraene

CycloocLaLeLraene ls noL planar
lL has alLernaung long (146 pm)
and shorL (133 pm) bonds
CyclobuLadlene sLablllzed
derlvauve has alLernaung
long (131 pm) &
shorL (133 pm) bonds
8oLh are __________________________. An ___________
subsLance ls one LhaL ls !!!!!!!!!!!! by cycllc con[ugauon






















Cycllc con[ugauon ls necessary, "#$ &'$ (#)*+,&$


kequ|rements for Aromanc|ty


noL
aromauc
aromauc
noL
aromauc
Antiaromatic
when square
Antiaromatic
when planar
Concluslon: MusL be some facLor ln addluon Lo cycllc
con[ugauon LhaL deLermlnes wheLher a molecule ls
aromauc or noL















Both undergo distortion to be more stable as non-aromatic species
ncke|'s ku|e:
ln order Lo be consldered aromanc,
a compound MUS1 be:
! Cycllc
! lanar
! lully con[ugaLed
! & # of e-s = 4. + 2

Among planar, monocycllc, compleLely con[ugaLed
polyenes, only Lhose wlLh 4& + 2 # elecLrons possess speclal
sLablllLy (are aromauc)
A SLrucLure ls annaromanc lf lL ls planar & fully con[ugaLed
wlLh 4& # elecLrons ln a cycllc fully con[ugaLed sysLem
8enzene!

#-L|ectron kequ|rement for Aromanc|ty


anuaromauc
aromauc
4 ! elecLrons 6 ! elecLrons 8 ! elecLrons
anuaromauc
Comp|ete|y Con[ugated o|yenes

aromauc
6 ! elecLrons,
compleLely con[ugaLed
noL
aromauc
6 ! elecLrons,
con[ugaLed, buL cycle
ls noL compleLe

P P
Wh|ch of the fo||ow|ng are aromanc ?
+
+
_

P P

Cyc|oheptatr|eny| Canon, 1ropy||um |on
lonlc
CovalenL
6 ! elecLrons & posluve charge delocallzed over 7
carbons
__________, very sLable called 1ropyllum lon

1ropyllum lon so sLable LhaL 1ropyllum bromlde ls lonlc
lnsLead of covalenL.
Compare Ac|d|nes of
Cyc|opentad|ene and Cyc|oheptatr|ene
p/
a
= 16
/
a
= 10
-16
p/
a
= 36
/
a
= 10
-36
Aromauc anlon
6 ! elecLrons
Anuaromauc
anlon
8 ! elecLrons
Cyc|opentad|en|de An|on
6 ! elecLrons delocallzed
over 3 carbons
negauve charge
dlspersed over 3 carbons
sLablllzed anlon
p/
a
= 16
very acldlc for a
hydrocarbon due Lo
resonance sLablllLy of Lhe
anlon
Can you show the L|ectron De|oca||zanon?
--
-

P
P
P
P
P
Ferrocene: An Organometallic Molecule
What is the hybridization of each heteroatom
for each of the above heterocyles ?
A sp B sp
2
C sp
3
Which of the following has a lone pair not
involved in resonance ?
A B C D
L All lone palrs are lnvolved ln resonance.
Which of the following
molecules are aromatic ?
.
_
+
A B C D