R EACTION I NTERMEDIATES

FUNDAMENTAL CONCEPTS IN ORGANIC REACION MECHANISMS

In an organic reaction, the organic molecule (known as substrate) reacts with an attacking reagent and leads
to the formation of the products. The reaction may take place in single step or in multiple steps. In a multiple
step reaction, the product of a step that takes part in the successive step is considered as an intermediate in
the overall reaction.

Ex:

B a n d C a re i n te r m e di a tes for t h e ove r a ll re actio n A  D .

T h e re a ctio n s t a k e pl ace d u e to elect ro n reorga n iz a tio n i n t h e re act a n t m olec u le. O n e or m ore

bo n ds a re b ro k e n , a n d a n ew bo n d or bo n ds a re for m e d i n t h e re a ctio n .

T h e det a iled st u dy of ste p wise descri p tio n of a re a ctio n , elect ro n m ove m e n t, e n e rge tic d u ri ng
bo n d b re a k i n g a n d bo n d for m a tio n a n d t h e de t ails of ti m e req u ire d for t h e steps, w h e n a
re a ct a n t is t r a n sfor m ed i n to t h e p rod u ct is ca lle d re a ctio n m ec h a n is m .

K i n e tics is t h e st u d y of re a ctio n r a tes. H ow fa st a re a ctio n goes is j u st a s i m por t a n t a s t h e

positio n of its eq u ili b ri u m . J u st bec a u se t h e r m ody n a m ics fa vors a re a ctio n (n ega tive  G )
does n ot n ecess a rily m e a n t h e re a ctio n will a ct u ally occ u r. F or ex a m ple, a m i x t u re of
m e t h a n e a n d c h lori n e does n ot re a ct if it is k e p t col d a n d d a r k .

RATE OF A REACTION
T h e r a te of a re a ctio n is a m e a s u re of h ow fa st t h e p rod u cts a p pe a r a n d t h e re a ct a n ts
dis a p pe a r. We c a n de te r m i n e t h e r a te by m e a s u ri ng t h e i n cre a se i n t h e co n ce n t r a tio n s of t h e
p rod u cts wit h ti m e, or t h e decre a se i n t h e co n ce n t r a tio n s of t h e re act a n ts wit h ti m e.
Re a ctio n r a tes depe n d on the co n ce n tr a tio n s of the re a ct a n ts. The gre a te r the
co n ce n t r a tio n s, t h e more ofte n t h e re a ct a n ts colli de a n d t h e gre a ter t h e c h a n ce of re a ctio n . A
r a te eq u a tio n (or r a te l a w) is t h e rel a tio n s h i p be t wee n t h e co n ce n t r a tio n s of t h e re a ct a n ts a n d
the obse rved re a ctio n r a te. E ach re a ctio n h as its ow n r a te eq u a tio n , de te r m i n e d

seem
32 REACTION INTERMEDIATES

ex pe ri m e n t ally by c h a n gi n g t h e co n ce n t r a tio n s of t h e re a ct a n ts a n d m e a s u ri ng t h e c h a nge i n

t h e r a te. F or e x a m ple, co n si de r t h e ge n e r a l re a ctio n
A  B  C  D
T h e re a ctio n r a te is u s u a lly p ropor tio n a l to t h e co n ce n t r a tio n s of t h e re a ct a n ts ([A] a n d [B])
r a ise d to so m e powe rs, a a n d b. W e c a n u se a ge n e r al r a te ex p ressio n to re p rese n t t h is
rel a tio n s h ip a s

r a te  k r  A   B 
a b

W h e re, k r is t h e r a te co n st a n t, a n d t h e v al u es of t h e powe rs (a a n d b) m u st be dete r m i n e d

ex pe ri m e n t ally. We c a n n ot g u ess or c a lc u l a te t h e r a te eq u a tio n fro m j u st t h e stoic h io m e try of
t h e re a ctio n . T h e r a te eq u a tio n depe n ds o n t h e m ec h a n is m of t h e re a ctio n a n d o n t h e r a tes of
t h e i n divi d u a l steps i n t h e m ec h a n is m .

Order of reaction
I n t h e ge n e r al r a te eq u a tio n , t h e powe r a is c a lled t h e or de r of t h e re a ctio n wit h respect to
re a ct a n t A , a n d b is t h e or de r of t h e re a ctio n wit h respect to B . T h e s u m of t h ese powe rs
(a  b) , is c a lled t h e ove r a ll or de r of t h e re a ctio n .

T h e most i m por t a n t fa ct to re m e m be r is t h a t t h e r a te eq u a tio n m u st be de te r m i n ed

ex pe ri m e n t ally. We c a n n ot p re dict t h e for m of t h e r a te eq u a tio n fro m t h e stoic h io m e t ry of t h e
re a ctio n . We dete r m i n e t h e r a te eq u a tio n ex pe ri m e n t a lly, a n d t h e n u se t h a t i n for m a tio n to
p ropose co n siste n t m ec h a n is m s.

Activation energy
E a c h re a ctio n h a s its ow n c h a r a cte ristic r a te co n st a n t, k r . Its v a l u e de pe n ds o n t h e
co n ditio n s of t h e re actio n , especi a lly t h e te m pe r a t u re. T h is te m pe r a t u re de pe n de n ce is
ex p resse d by t h e A r r h e n i u s eq u a tio n ,
k r  A e E a / RT

W h e re
A  a co n st a n t (t h e "freq u e n cy fa ctor ")
E a  a ctiv a tio n e n e rgy
R  t h e ga s co n st a n t, 8 . 3 1 4 J / K m ol (1 . 9 8 7 c a l / K m ol)
T  t h e a bsol u te te m pe r a t u re

noooooo
 REACTION INTERMEDIATES 33

T h e A r r h e n i u s eq u a tio n i m plies t h a t t h e r a te of a re a ctio n depe n ds o n t h e fr a ctio n of

m olec u les wit h k i n e tic e n e rgy of a t le a st E a . F ig u re s h ows h ow t h e dist ri b u tio n of k i n etic
e n e rgies i n a s a m ple of a ga s de pe n ds o n t h e te m pe r a t u re.

T h e a ctiv a tio n e n e rgy E a re p rese n ts t h e e n e rgy diffe re n ce be twee n t h e re a ct a n ts a n d t h e

t r a n sitio n st a te, t h e h ig h est-e n e rgy st a te i n a m olec u l a r collisio n t h a t le a ds to re a ctio n . I n
effect, t h e a ctiv a tio n e n e rgy is t h e b a r rie r t h a t m u st be ove rco m e for t h e re a ctio n to t a k e
pl a ce. T h e v a l u e of E a is a lw a ys positive, a n d its m agn it u de depe n ds o n t h e rel a tive e n e rgy of
t h e t r a n sitio n st a te. T h e te r m t r a n sitio n st a te i m plies t h a t t h is co nfig u r a tio n is t h e t r a n sitio n
bet wee n t h e re act a n ts a n d p rod u cts, a n d t h e m olec u les c a n eit h e r go o n to p rod u cts or
re t u r n to re a ct a n ts. U n li k e t h e re a ct a n ts or p rod u cts, a t r a n sitio n st a te is u n st a ble a n d
c a n n ot be isol a te d. It is n ot a n i n te r m edi a te, bec a u se a n i n te r m e di a te is a species t h a t ex ists
for so m e fi n ite le ngt h of ti m e, eve n if it is ve ry s h or t. A n i n te r m e di a te h a s a t le ast so m e
st a bility, b u t t h e t r a n sitio n st a te is a t r a n sie n t o n t h e p a t h fro m o n e i n te r m e di a te to a n ot h e r.
T r a n sitio n st a tes h a ve h ig h e n e rgies bec a u se bo n ds m u st begi n to b re a k before ot h e r bo n ds
c a n for m .

e
34 REACTION INTERMEDIATES

T h e a bove eq u a tio n t h e re a ctio n of a c h lori n e r a dic al wit h m e t h a n e, t h e t r a n sitio n st a te

s h ows t h e C - H bo n d p a r ti a lly b ro k e n a n d t h e H - C l bo n d p a r ti ally for m e d. T r a n sitio n st a tes
a re ofte n e n closed b y b r a c k ets to e m p h a size t h eir t r a n sie n t n a t u re.
Reaction-energy Diagram

T h e co n ce p ts of t r a n sitio n st a te a n d a ctiv a tio n e n e rgy a re e a sie r to u n de rst a n d gr a p h ica lly.

F ig u re s h ows a re a ctio n -e n e rgy di agr a m for a o n e-step exot h e r m ic re a ctio n . T h e ve r tic a l a x is
of t h e e n e rgy di agr a m re p rese n ts t h e tot al pote n ti al e n e rgy of a ll t h e species i n volve d i n t h e
re a ctio n . T h e h orizo n t a l a xis is c a lle d t h e re a ctio n coor di n a te. T h e re a ctio n coor d i n a te
sy m bolizes t h e p rogress of t h e re a ctio n , goi n g fro m t h e re a ct a n ts o n t h e left to t h e p rod u cts
o n t h e rig h t. T h e t r a n sitio n st a te is t h e h ig h est poi n t o n t h e gr a p h , a n d t h e a ctiv a tio n e n e rgy
is t h e e n e rgy diffe re n ce be twee n t h e re act a n ts a n d t h e t r a n sitio n st a te. T h e h e a t of re a ctio n (
 H 0 ) is t h e diffe re n ce i n e n e rgy bet wee n t h e re a ct a n ts a n d t h e p rod u cts. If a c a t a lyst were
a d ded to t h e re actio n , it wo u l d cre a te a t r a n sitio n st a te of lowe r e n e rgy, t h e re by lowe ri ng t h e
a ctiv a tio n e n e rgy. A d ditio n of a c a t a lyst wo u l d n ot c h a nge t h e e n ergies of t h e re a ct a n ts a n d
p rod u cts, h oweve r, so t h e h e a t of re a ctio n a n d t h e eq u ili b ri u m co n st a n t wo u l d be u n affecte d.

Rate determining step

T h e r a te-li m iti ng step i n a m u ltistep re a ctio n , e a c h ste p h a s its ow n c h a r a cte ristic r a te. T h e re
c a n be o n ly o n e ove r all re a ctio n r a te, h oweve r, a n d it is co n t rolled b y t h e r a te-li m iti ng ste p
(a lso c alled t h e r a te-dete r m i n i ng ste p). I n ge n e r al, t h e h igh est e n e rgy step of a m u ltistep
re a ctio n is t h e " bot tle n ec k ," a n d it de te r m i n es t h e ove r all r a te. H ow c a n we tell w h ic h ste p is
r a te li m iti n g? If we h ave t h e re a ctio n -e n e rgy di agr a m , it is si m ple: T h e h ig h est poi n t i n t h e
e n e rgy di agr a m is t h e t r a n sitio n st a te wit h t h e h ig h est e n e rgy-t h e t r a n sitio n st a te for t h e
r a te-li m iti n g ste p.

nodes
 REACTION INTERMEDIATES 35

TYPES OF BOND FISSION

T h e bo n d m a y b re a k (fissio n) i n t h e t wo w a ys

1. Heterolytic fission
H e te roly tic fissio n is u n sy m m e t ric a l so t h a t o n e of t h e fr ag m e n ts t a k es bot h t h e
elect ro n s of t h e s h a red p a ir le a vi ng n o n e o n t h e ot h e r. T h is res u lts i n to two c h a rge d
p a r ticles. O n e a to m h a s a sex te t of elect ro n s a n d t h e refore, h a s a positive c h a rge
w h ile ot h e r will h a ve a v a le n ce octe t wit h a t le a st o n e lo n e p a ir a n d t h e refore, h a s a
n ega tive c h a rge. T h is s h ift of elect ro n p a ir is s h ow n by a c u rve d a r row, ( ),
w h ic h st a r ts fro m t h e m i d dle of t h e bo n d t h a t b re a k s a n d e n ds o n t h e a to m to
w h ic h t h e elect ro n p a ir s h ifts.
T h e species t h a t h a s a sex te t a t t h e c a r bo n a n d positively c h a rged is c alled a s
c a r boc a tio n (e a rlie r c alled c a r bo n i u m io n). T h e species t h a t h as a c a r bo n wit h t h e
s h a re d p a ir of elect ro n s a n d c a r ryi ng a n ega tive c h a rge is c a lled c a r b a n io n .
Ex:

2. Homolytic fission
I n h o m olytic fissio n , t h e cle av age of cov a le n t bo n d be twee n two a to m s t a k es pl a ce
i n s u c h a w a y t h a t e a c h a to m re t a i n s o n e elect ro n of t h e s h a red p a ir. T h is is a
sy m m e t ric al fissio n a n d le a ds to t h e for m a tio n of n e u t r a l species (a to m s or gro u p
of a to m s) h a vi ng u n p aire d elect ro n s. T h ese species a re c a lle d free radicals . T h e free

area
 36 REACTION INTERMEDIATES

r a dic a ls a re de n ote d by p u t ti n g dot ove r t h e sy m bol of a to m or gro u p of a to m s. T h e

si ngle elect ro n move m e n t is s h ow n by two "fis h h oo k s " ( ) st a rti ng fro m t h e
m i d dle of bo n d a n d e n di ng o n eit h e r a to m .
Ex:

Reaction intermediates
T h e ty pes of species for m ed d u e to eit h e r h ete roly tic or h e m olytic bo n d cle a v age a re c a lled
re a ctio n i n te r m e di a tes. T h ese a re co m ple tely co n s u m e d to give t h e p rod u cts. Nor m a lly t h ey
h a ve te m por a ry existe n ce b u t c a n be isol a ted u n de r specific co n ditio n s.

TYPES OF REACTION INTERMEDIATES

I. Carbocation
T h ese re a ctio n i n te r m e di a tes a re for m e d i n seve r a l k i n ds of orga n ic re a ctio n s.
T h e species t h a t h as a sex tet a t t h e c a r bo n a n d positively c h a rge d is c a lle d a s c a r boc a tio n .

Structure of carbocation
T h e c a r bo n a to m i n c a r boc a tio n is sp 2 h y d ri dised. T h e t h ree sp 2 h y b ri d orbit a ls for m t h ree

-bo n ds wit h h y d roge n or ot h e r c a r bo n a to m s of a l k yl gro u ps. T h e u n h y b ri dised p -or bit a l of

c a r bo n re m ai n s v a c a n t. Si n ce it i n volves sp 2 h y b ri diz a tio n , its st r u ct u re is t rigo n a l pl a n a r
wit h a bo n d a ngle 1 2 0  .

Stability of carbocation
T h e c a r boc a tio n s a re elect ro n deficie n t. If t h e elect ro n de n sity o n positively c h a rge d c a r bo n of
c a r boc a tio n i n cre a ses (positive c h a rge decre ases), d u e to elect ro n displ a ce m e n t effects, t h e n
t h e st a bility of c a r boc a tio n i n cre a ses. T h e st a bility of v a rio u s c a r boc a tio n s c a n be ex pl ai n ed
b y t h e elect ro n displ a ce m e n t effects.

adore
 REACTION INTERMEDIATES 37

i) Stabilization by both the +I-effect and the hyperconjugative effect

A l k yl gro u p st a bilizes c a r boc a tio n s b y bot h t h e +I-effect a n d t h e
h y pe rco n j u ga tive effect.

T h e st a bility or de r of t h e followi ng c a r boc a tio n s is

T h is or de r of st a bility c a n be e a sily ex pl a i n ed o n t h e b asis of h y perco n j u ga tio n .

I n c a se of te r ti a ry b u tyl c a r boc a tio n  3  t h e re a re n i n e - h y d roge n a to m s a n d h e n ce

n i n e h y pe rco n j u ga tio n st r u ct u res a re possi ble

Six m ore s u c h st r u ct u res fro m t h e ot h e r t wo m e t h yl gro u ps c a n be d r a w n .

O n t h e ot h e r h a n d, i n isop ropyl c a r boc a tio n  2  , t h e re a re six - h y d roge n a to m s a n d

h e n ce six h y pe rco n j u ga tio n st r u ct u res a re possi ble

I n a si m il a r w a y, e t h yl c a r boc a tio n 1  h a s o n ly t h e re - h y d roge n a to m a n d h e n ce

o n ly t h ree h y pe rco n j u ga tio n st r u ct u res possi ble.

H oweve r, n o h y pe rco n j u ga tio n st r u ct u re ca n be d r a w n for m e t h yl, C H 3 c a r boc a tio n .

T h u s, i n ge n e r a l, gre a te r t h e n u m be r of a l k yl gro u ps a t t a c h ed to a positively c h a rged
c a r bo n a to m , t h e gre a te r is t h e h y pe rco n j u ga tio n i n te r a ctio n a n d st a bilis a tio n of t h e
c a tio n .

T h e “–I” gro u ps dest a bilize c a r boc a tio n .

ii) Stabilization by resonance

+ R gro u ps st a bilize t h e c a r boc a tio n s.
a) W h e n t h e positive c h a rge c a r bo n is i n co n j u ga tio n wit h a do u ble bo n d t h e st a bility is
gre a te r bec a u se of i n cre a sed deloc aliz a tio n d u e to reso n a n ce a n d bec a u se t h e positive
c h a rge is sp re a d ove r two a to m s i n ste a d of bei ng co n ce n t r a te d o n o n e.

0
38 REACTION INTERMEDIATES

b) C a n o n ic al for m s c a n be d r a w n for be n zylic ca tio n s, si m il a r to t h ose s h ow n

a bove for a llylic c a tio n s.

M ore t h e n u m be r of c a n o n ic al for m s for c a r boc a tio n , gre a te r t h e st a bility.

So di a ryl m e t h yl a n d tri a ryl m e t h yl c a tio n s a re still m ore st a ble. Triryl m e t h yl c a tio n s
a re p ropelle r-s h a pe d, t h o u gh t h e ce n t r a l c a r bo n a n d t h e t h ree ri n gs co n n ecte d to it
a re i n a pl a n e d u e to ste ric h i n d r a n ce be twee n t h ree be n ze n e ri ngs.
S t a bility or de r of a ryl m e t h yl c a tio n s

‘+ R’ gro u ps a tt a c h ed to ri ng i n cre a ses st a bility of c a r boc a tio n s w h e re a s ‘–R’ gro u ps

a t t a c h e d to ri ng decre a ses t h e st a bility of c a r boc a tio n s.
Ex:
1)

S t a bility or de r is (ii) > (i) > (iii).

we
 REACTION INTERMEDIATES 39

2)

S t a bility or de r is (ii) > (iii) > (iv) > (v) > (i).
T h is or de r c a n be ex pl a i n e d by t h e n u m be r of h y pe rco n j u ga tive
st r u ct u res possi ble fro m t h e s u bstit u e n t.
c) C yclop rop yl m e t h yl c a tio n s a re eve n m ore st a ble t h a n t h e be n zyl c a tio n s.

T h is speci al st a bility i n cre a ses wit h e a c h a d ditio n a l cyclop ropyl gro u p, is a res u lt of
co n j u ga tio n be twee n t h e be n t or bit a ls of t h e cyclop rop yl ri ngs a n d t h e v ac a n t ‘p’
or bit al of t h e c a tio n ic c a r bo n .
N m r a n d ot h e r st u dies h a ve s h ow n t h a t t h e va c a n t ‘p’ or bit a l lies p a r a llel to t h e C—2,
C—3 bo n d of t h e cyclop rop a n e ri ng a n d n ot pe r pe n dic u l a r to it. I n t h is respect t h e
geo m et ry is si m il a r to t h a t of cyclop rop a n e ri n g co n j u ga te d wit h a do u ble bo n d.

C yclop rop yl m e t h yl c a tio n

H e n ce st a bility or de r is

and
40 REACTION INTERMEDIATES

d) T h e st a bility of c a r boca tio n i n cre a ses w h e n c a tio n ic ce n te r is co n n ecte d to h e te ro a to m

b a ri n g a n u n s h a re d p a ir e.g., ox yge n , n it roge n or h a loge n . S u c h io n s a re st a bilized
b y reso n a n ce.

1)

2)

Examples on stability order of carbocations.

1)

S t a bility or de r is (i) > (ii) > (iii) > (iv).

S t a bility of (i) and (ii) is ex pl a i n e d on the b asis of bot h +I effect and

h y pe rco n j u ga tio n w h ere a s (iii) a n d (iv) is o n ly b a se d o n +I effect.

2)

S t a bility or de r is (iv) > (iii) > (ii) > (i).

3)

S t a bility or de r is (ii) > (i).

even
 REACTION INTERMEDIATES 41

4)

S t a bility or de r is (i) > (ii) > (iii) > (iv) > (v) > (vi).
T h e st a bility or de r is s u p por te d b y t h e st a biliz a tio n e n e rgies of t h e a bove st r u ct u res
rel a tive to C H 3 c a r boc a tio n .

Structure Stabilization energy (kcal/mol)

(i) 114

(iii) 1 0 2.2

(iv) 9 1.6

(v) 91

(vi) 7 1.5

5)

S t a bility or de r is (i) < (ii).

E vi de n ce for t h e h y pe rco n j u ga tio n ex pl a n a tio n is t h a t t h e eq u ilib ri u m co n st a n t for t h is

re a ctio n is 1.9 7, s h owi n g t h a t (ii) is m ore st a ble t h a n (i).

 C D 3 3 C    C H 3  3 C H 
  C H 3 3 C    C D 3 3 C H
(i) (ii)
K eq  1 .9 7  0 .2 0

6)

S t a bility or de r is (i) > (ii) > (iii).

mood
 42 REACTION INTERMEDIATES

F or a to m s h a vi n g differe n t h y b ri dis a tio n s, gre a te r be t h e ‘s’ c h a r a cte r of h y b ridis a tio n ,

gre a te r be t h e elect ro n ega tivity of a to m .

So sp- h y b ri dise d c a r bo n a to m c a n n ot b a re positive c h a rge.

7)

S t a bility or de r is (ii) > (i) > (iii).

C a r boc a tio n s a re diffic u lt or i m possible to for m a t b ri dge h e a d a to m s i n [2.2.1]

syste m s, w h e re t h ey ca n n ot be pl a n a r. H oweve r, l a rge r b ri dge h e a d io n s c a n ex ist.

General stability order of carbocations

INTEXT Q UESTIONS

1 1. W rite t h e st a bility or de r for t h e followi n g.

a)

doors
 REACTION INTERMEDIATES 43

b)

c)

d)

e)

f)

off
 44 REACTION INTERMEDIATES

Ans. S t a bility or de r is
a) (iii) > (ii) > (i) b) (iii) > (ii) > (i) > (iv) c) (iv) > (ii) > (iii) > (i)
d) (v) > (i) > (ii) > (iii) > (iv) e) (iii) > (iv) > (ii) > (i) f) (i) > (ii) > (iii).

Generation of carbocations
i) From alkyl halides
A l k yl h a lides o n t re a t m e n t wit h Le wis a cids s u c h a s A l C l 3 , B F 3 , F e C l 2 , Z n C l 2 a n d

S n C l 4 , e tc., ge n e r a te c a r boca tio n i n te r m e di a tes.

Mechanism

ii) From Alcohols

A lco h ols ge n e r a te c a r boc a tio n s i n p rese n ce of p rotic a ci d m e di u m or i n Le wis a ci dic
m e di u m .

noooooo
 REACTION INTERMEDIATES 45

iii) From Alkenes / Alkynes

A l k e n es a n d Al k y n es ge n e r a te c a r boc a tio n s i n p rese n ce of p rotic a ci d m e di u m .

iv) From 1° amine

H N O 2 is u n st a ble h a s to be p re p a re d fres h ly.

N a N O 2  H C l  H N O 2  N a C l

v) From Alkanes

Fate of carbocations
i) C a r boc a tio n s co m bi n e wit h a n u cleop h ile to for m p rod u cts.

Ex:

1)

2)

ii) So m e c a r boc a tio n s a ct a s B ro n ste d a ci d to lose a p roto n a n d p rod u ce a l k e n e.

e
46 REACTION INTERMEDIATES

iii) 1  or 2  c a r boc a tio n s ofte n u n de rgo W ag n e r-M ee rwei n re a r r a n ge m e n t by an

a n io n t ropic 1,2-s h ift of a h y d ri de or a n a l k yl a n io n .

M igr a tory a p tit u de i n W ag n e r-M ee rwi n re a r r a n ge m e n t is

H > Ph > R

R : 3° > 2° > 1° (w h e n R is a l k yl)

Ex:
1)

2)

3)

Re a r r a n ge m e n t c a n occ u r a n y n u m be r of ti m es a s lo n g a s t h e p rod u ct is m ore

st a ble t h a n e a rlie r.

4)

down
 REACTION INTERMEDIATES 47

5)

II. Carbanion
T h ese a re t h e a n io n s of c a r bo n ge n e r a ted b y re m ov a l of a gro u p a t t a c h e d to a C - a to m wit h o u t
re m ovi n g t h e bo n di ng elect ro n s. T h e C - a to m , t h e refore, c a r ries a n u n s h a red elect ro n p a ir
i.e., a n ega tive c h a rge. T h e refore, t h e octe t of t h e C - a to m is co m plete. T h e p a re n t c a r b a n io n

is t h e m et h yl a n io n .

Structure of carbanion

Si m ple c a r b a n io n s li k e a re isoelect ro n ic wit h N H 3 . I n t h ese species, t h e ce n t r a l C - a to m

is sp 3 - h y b ri dize d, a n d t h e s h a pe is py r a m i d a l.

T h e t wo e n a n tio m e ric for m s t h a t m a y be possi ble for a sy m m etric c a r b a n io n s of t h e ty pe

a re i n r a pi d eq u ili b ri u m for w h ic h n o op tic a l a ctivity is s h ow n by s u c h a n io n s (d u e

to t u n n el effect).

It
48 REACTION INTERMEDIATES

B u t t h e geo m e t ries of c a r b a n io n s st a bilize d b y co n j u ga tio n a re pl a n a r d u e to a C = C bo n d

for m a tio n a n d t h e h y b ri dis a tio n is sp 2 .

Stability of carbanion
i) Conjugation of the unshared pair with an unsaturated bond.
a) I n c a ses w h e re a do u ble or t ri ple bo n d is loca te d  to t h e c a r b a n io n ic c a r bo n ,
t h e io n is st a bilize d b y reso n a n ce i n w h ic h t h e u n s h a re d p air ove rl a ps wit h t h e
-elect ro n s of t h e do u ble bo n d. T h is fa ctor is respo n sible for t h e st a bility of t h e
a llylic a n d be n zylic ty pes of c a r b a n io n s.

b) C a r b a n io n a t t a c h ed wit h a ro m a tic ri n gs.

D i p h e n yl m e t h yl a n d t ri p h e n yl m e t h yl a n io n s a re still m ore st a ble. H e n ce t h e

st a bility or de r is

‘–R’ gro u ps o n a ro m a tic ri n gs i n cre ase st a bility of c a r b a n io n .

code
 REACTION INTERMEDIATES 49

S t a bility or de r is (ii) > (iv) > (iii) > (i).

‘+ R’ gro u ps o n a ro m a tic ri n gs decre a se st a bility of c a r b a n io n .

S t a bility or de r is (iii) > (i) > (ii) > (iv).

c) W h e re t h e c a r b a n io n ic c a r bo n is co n j u ga ted wit h a c a r bo n–ox yge n or c a r bo n–n it roge n

m u lti ple bo n d (Y = O or N), t h e st a bility of t h e io n is gre a te r t h a n t h a t of t h e
t ri a ryl m e t h yl a n io n s, si n ce t h ese elect ro n ega tive a to m s a re be tte r c a p a ble of be a ri n g a
n ega tive c h a rge t h a n ca r bo n .

A n it ro gro u p is p a r tic u l a rly effective i n st a bilizi ng a n ega tive c h a rge o n a n a dj a ce n t

c a r bo n , a n d t h e a n io n s of si m ple n it ro a l k a n es c a n ex ist i n w a te r.
50 REACTION INTERMEDIATES

Ex:

S t a bility or de r is (ii) > (i).

Note
I n co n t r a st to t h e st a bilit y of cyclop rop yl m e t h yl c a tio n s, t h e cyclop rop yl gro u p e xe rts
o n ly a we a k st a bilizi n g effect o n a n a dj a ce n t c a r b a n io n ic c a r bo n .

ii) Stability due to hybridisation

C a r b a n io n s st a bility i n cre a ses wit h a n i n cre a se i n t h e a mo u n t of ‘s’ c h a r a cte r of t h e
h y b ri dis a tio n of c a r bo n .

T h u s t h e or de r of st a bility is

iii) Stability due to aromaticity

C e r t a i n c a r b a n io n s a re st a ble d u e to t h eir a ro m a tic c h a r a cte r.

Examples on stability order of carbanions.

1) T h e st a bility of c a r b a n io n s c a n n ot be e x pl a i n e d by h y pe rco n j u ga tio n . T h e +I a l k yl
gro u ps decre ases t h e st a bility of c a r b a n io n .

S t a bility or de r is (i) > (ii) > (iii) > (iv).

a
 REACTION INTERMEDIATES 51

2)

S t a bility or de r is (ii) > (i) > (iii) > (iv).

3)

S t a bility or de r is (ii) > (iii) > (iv) > (i).

4)

+ R effect d u e to h y pe rco n j u ga tio n .

S t a bility or de r is (i) > (iii) > (iv) > (ii).

5)

S t a bility or de r is (ii) > (i) > (iii).

I n st r u ct u re (ii) t h e n ega tive c h a rge o n c a r bo n i n volves i n reso n a n ce wit h t h e v ac a n t
or bit al of s u l p h u r.

e
52 REACTION INTERMEDIATES

6)

I n st r u ct u re (i) t h e re is n o b a c k bo n d for m a tio n be twee n c a r bo n a n d fl u ori n e a s t h ere

is n o v a c a n t or bit al o n fl u ori n e. I n st r u ct u re (ii) t h e re is b a c k bo n d for m a tio n be twee n
c a r bo n a n d fl u ori n e d u e to 2 p-3 d ove rl a p pi ng.
H e n ce t h e st a bility or de r is (ii) > (i).

7)

T h e s-c h a r a cte r of C—H bo n d is (i) > (ii) > (iii), so a cidic c h a r a cte r of i n cre a ses t h e n
t h e st a bility or de r is (i) > (ii) > (iii).

8)

S t a bility or de r is (i) > (ii) > (iii) > (iv).

General stability order of carbanions

N it roc a r b a n io n s > Active m et h yle n e > A ro m a tic a n io n s > C a r b a n io n s wit h o n ly o n e (–I) gro u p

> E t h yl > Isop ropyl > Te r ti a ry b u tyl.

Generation of carbanions
i) C sp3 — H bo n d is n ot a ci dic d u e to co m p a r a ble elect ro n ega tivity of C -a to m a n d
H - a to m . B u t w h e n a st ro n g elect ro n -wit h d r a wi ng gro u p or gro u ps a re a t t a c h ed to
s u c h a C - a to m , t h e a ci dity of t h e H - a to m i n cre a ses. S u c h co m po u n ds, pop u l a rly
k n ow n a s a ctive m e t h yle n e or a ctive m e t h yl co m po u n ds or c a r bo n a ci ds, o n t re a t m e n t

awake
 REACTION INTERMEDIATES 53

wit h st ro n g b a ses li k e sodi u m a l k ox i des or lit h i u m diisop ropyl a m i de, (L D A) for m

c a r b a n io n s t h a t a re st a bilize d b y t h e —R-effect of elect ro n -wit h d r a wi n g gro u ps li k e
—C H O , —C O O R, —C N, , a n d so o n .
Ex:

1)

2)

ii) S t ro ngly re d u ci n g m et a ls li k e N a or Li or Mg c a n co n ve r t a l k yl h a lides to al k yl sodi u m

or a l k yl lit h i u m or G rig n a r d re age n t.

iii) C a r b x yl a te io n s o n st ro ng h e a ti ng p rod u ce ca r b a n io n s.

Fate of carbanions
i) C a r b a n io n s ofte n a ct as n u cleop h iles to re act wit h elect rop h ilic species.
Ex:

1)

see
54 REACTION INTERMEDIATES

2)

3)

ii) C a r b a n io n c a n a ct a s a b a se a n d a bst r a ct h y d roge n s.

Ex:

1)

2)

iii) Re- a r r a n ge m e n ts a re q u ite u n co m mo n ex cep t a llyl (or) si m il a r s h ifts. T h e re a re few

c a ses k n ow n i n volvi n g t h e p h e n yl s h ifts.
Ex:

1)

2)

3)

war
 REACTION INTERMEDIATES 55

4)

Note: A l k yl s h ift does n ot h a p pe n i n c a r b a n io n s.

III. Free radical

A free r a dic al m a y be defi n ed a s a n a to m or gro u p of a to m s h a vi ng a n u n p a ire d elect ro n .
T h ese a re p rod u ced d u ri ng t h e h o moly tic fissio n of a cov ale n t bo n d.
T h ese free r a dic als a re ve ry re a ctive. T h is is bec a u se of t h e fact t h a t t h ey h a ve st ro ng
te n de n cy to p a ir u p t h eir u n p aire d elect ro n wit h a n ot h e r elect ro n fro m w h e reve r a v a il a ble.
T h ese a re ve ry s h or t live d a n d occ u r o n ly a s re a ctio n i n te r m e di a tes d u ri ng re a ctio n s.
Structure of free radical
T h e c a r bo n a to m i n a l k yl free r a dic als i n volves sp 2 h y b ri dis a tio n . T h e refore, it h a s a pl a n a r

st r u ct u re. T h e t h ree h y b ri d or bit a ls a re u se d i n t h e for m a tio n of t h ree -bo n ds wit h t h ree

H - a to m s or a l k yl gro u p. T h e u n p aire d elect ro n is p rese n t i n u n h y b ri dised p-or bit a l.

Pl a n a r st r u ct u re of free r a dic al
I n so m e free r a dic a ls t h e h y b ri diz a tio n is sp 3 , w h ic h wo u l d m a k e t h e st r u ct u re py r a m i d al

a n d pl a ce t h e od d elect ro n i n a n sp 3 or bit al.

T h e a v a il a ble evi de n ce i n dic a tes t h a t a lt h o u gh si m ple al k yl free r a dic a ls p refe r a pl a n a r or
n e a r-pl a n a r s h a pe, t h e e n e rgy diffe re n ce betwee n a pl a n a r a n d a p y r a m i d a l free r a dic a l is n ot
gre a t.
H oweve r, free r a dic a ls i n w h ic h t h e c a r bo n is co n n ected to a to m s of h igh elect ro n ega tivity,

for ex a m ple, " C F 3 " , p refe r a p y r a m i d a l s h a pe; i n cre a si ng t h e elect ro n ega tivity i n cre a ses t h e
devi a tio n fro m pl a n a rity. C yclop ropyl r a dic a ls a re also p y r a m i d a l. F ree r a dic a ls wit h
reso n a n ce a re defi n itely pl a n a r, a lt h o u gh t rip h e n yl m et h yl-ty pe r a dic a ls a re p ropelle r-s h a ped,
li k e t h e a n a logo u s c a rboc a tio n s.

e
56 REACTION INTERMEDIATES

Stability of free radicals

T h e c a r bo n free r a dica ls a re elect ro n deficie n t. If t h e elect ro n de n sity o n c a r bo n i n cre a ses,
t h e st a bility of c a r bo n free r a dic als i n cre a ses. W it h reso n a n ce (h y pe rco n j u ga tio n or + R effect)
a n d +I effect t h e st a bility of c a r bo n free r a dica ls i n cre a ses.
i) S t a biliz a tio n of free r a dic a ls b y h y pe rco n j u ga tio n a n d +I effect.

T h e st a bility or de r is (i) > (ii) > (iii) > (iv).

T h is or de r of st a bility c a n e a sily be ex pl ai n ed o n t h e b a sis of h y perco n j u ga tio n . L a rger

t h e n u m be r of a l k y gro u ps a tt a c h ed to t h e c a r bo n a to m c a r ryi ng t h e od d elect ro n ,
gre a te r is t h e deloc a lis a tio n of t h e od d elect ro n a n d h e n ce more st a ble is t h e free
r a dic a l.

ii) S t a biliz a tio n b y reso n a n ce.

a)

M ore t h e n u m be r of reso n a n ce st r u ct u res gre a te r be t h e st a bility. Reso n a n ce

st r u ct u res of (i) a re more t h a n reso n a n ce st r u ct u res of (ii).
H e n ce st a bility or de r is (i) > (ii).

b)

T h e st a bility or de r is (i) > (ii).

T h o u gh reso n a n ce st r u ct u res of (ii) a re more t h a n reso n a n ce st r u ct u re (i), t h e
st a bility of (ii) is less t h a n (i). T h is c a n be ex pl a i n ed b y t h e bo n d dissoci a tio n
e n e rgies.

a
 REACTION INTERMEDIATES 57

The bond dissociation energies of some free radicals.

(Lesser is the dissociation energy more is the stability)

Bond dissociation energy

[Link] Free radical
(kJ / mol)
i) 361

ii) 364

iii) 368

iv) 400

v) 401

vi) ~ 401

vii) ~ 401

viii) 417
i x) 419
x) 438
x i) C yclop rop yl 444
x ii) 444
x iii) 446
x iv) 464

INTEXT Q UESTIONS
1 2. W rite t h e st a bility or de r for t h e followi n g.

a)

C
 58 REACTION INTERMEDIATES

b)

c)

d)

Ans. S t a bility or de r is
a) (i) > (ii) > (iii). b) (iii) > (iv) > (ii) > (i). c) (iii) > (i) > (ii). d) (i) > (ii) > (iii) > (iv)

Generation of free radicals

i) T h e r m olysis or p h otolysis of h a loge n s, orga n ic pe rox ides a n d a zo co m po u n ds
ge n e r a tes free r a dic a ls.

Ex:

1)

2)

3)

4)

war
 REACTION INTERMEDIATES 59

5)

6)

Pe roxi des a n d AI B N a re ge n e r ally u sed a s free r a dic al ge n e r a tors fro m ot h e r

m olec u les a n d ofte n t h is t rigge rs free r a dic a l c h a i n re a ctio n s.

Ex:

7)

Mechanism

ii) E lect rolysis of c a r box yl a te io n (or) K ol be’s elect rolysis.

Fate of a radical

i) R a dic a ls u n de rgo di m e ris a tio n .

See
60 REACTION INTERMEDIATES

ii) R a dic a ls c a n re act wit h a m olec u le.

iii) R a dic a ls c a n a bst r a ct a n ot h e r a to m or gro u p, u s u a lly a h y d roge n a to m .

iv) R a dic a ls u n de rgo disp ropor tio n a tio n re a ctio n s.

v) A d ditio n to m u lti ple bo n ds (do u ble or t ri ple bo n ds).

T h e r a dic a l for m e d h ere m a y a d d to a n ot h e r do u ble bo n d, e tc. T h is is o n e of t h e c h ief

m ec h a n is m s for vi n yl poly m e riz a tio n .

vi) Re a r r a n ge m e n ts a re q u ite u n co m m o n i n r a dic a ls b u t a llyl s h ift a n d re a r r a n ge m e n ts

i n volvi n g h ete ro a to m s li k e C l, B r e xist.

Mechanism

a
 REACTION INTERMEDIATES 61

IV. Carbenes
C a r be n es a re n e u t r a l re a ctio n i n te r m edi a tes co n t ai n i ng a biv a le n t C - a to m i n w h ic h t h e
C - a to m is cov ale n tly bo n de d to two ot h er gro u ps or a to m s a n d h a s t wo ot h e r v ale n ce
elect ro n s dist ri b u ted bet wee n t h e two n o n -bo n di ng or bit a ls. If t h ese t wo elect ro n s re m a i n
spi n p a ire d, c a r be n e is c a lle d a si nglet c a r be n e. If t h eir spi n s re m a i n p a r a llel, i t is c a lle d a
t ri plet c a r be n e.

Structure of carbene
T h e C - a to m i n si nglet c a r be n e is sp 2 - h y b ridized i n w h ic h t h e spi n -p a ire d elect ro n s occ u py

a n sp 2 or bit al. T h e s h a pe of s u c h c a r be n es is, t h e refore, pl a n a r. O n t h e ot h e r h a n d, t h e

C - a to m i n m a n y t ri plet c a r be n es is sp - h y b ridize d wit h o n e elect ro n e a c h wit h p a r a llel spi n i n
t h e re m a i n i ng t wo u n h y b ri dize d p-or bit a ls. T h ese c a r be n es h a ve a li n e a r s h a pe. H oweve r,
be n t t ri ple t c a r be n es a re also k n ow n w h e re t h e C - a to m is sp 2 - h y b ri dize d, a n d t h e two n o n -

bo n di ng elect ro n s occ u p y a n sp 2 - h y b ri d or bit als a n d a n u n h y b ri dized p-or bit a l wit h p a r a llel

spi n .

Ite
62 REACTION INTERMEDIATES

S pi n m u lti plicity = 2 S + 1 = 2(0) + 1 = 1.

S pi n m u lti plicity = 2 S + 1 = 2(1) + 1 = 3.

I n si m ple a l k yl c a r be n es t riplet is m ore st a ble t h a n si n glet bec a u se e n ergy of ~ 2 – 1 0

k c a l / m ol is req u ired for p a iri n g elect ro n s. B u t i n di h a lo c a r be n es si n glet is m ore
st a ble t h a n t riplet c a r be n es bec a u se overl a p pi n g of e m p ty p-or bit a l o n c a r bo n wit h
u n s h a red elect ro n p a ired p -or bit a l of h a loge n .
Ex: 
 C F 2 ,  C C l 2 ,  C B r2 ,  CI 2

C F 2   C C l 2   C B r2   CI 2


T h e S t a bility or de r is
2p  2p 2p  3p 2p  4p 2p  5 p

Generation of carbenes
i) I n -eli m i n a tio n , a c a r bo n loses a gro u p wit h o u t its elect ro n p air, u s u a lly a p roto n ,
a n d t h e n a gro u p wit h its p a ir, u s u a lly a h a lide io n .
Ex:

1)

Mechanism

are
 REACTION INTERMEDIATES 63

2)


 C C l F is m ore st a ble t h a n 
 C C l 2 a n d C l  is be tte r le a vi ng gro u p.

3)

ii) D ec a r box yl a tio n .

Mechanism

iii) P h otolysis / py rolysis of k e to n e.

Mechanism

iv) P h otolysis / py rolysis of di a zo a l k a n es.

Mechanism

a
64 REACTION INTERMEDIATES

v) P h otolysis of a ziri di n e.

vi)

Fate of a carbene
C a r be n es u n de rgo a va riety of re a ctio n s. T h e sy n t h e tic ally i m por t a n t o n es a re liste d below
i) D i m e ris a tio n of c a r be n es.

ii) I n se r tio n re a ctio n s.

A n u n u s u a l re a ctio n of c a r be n es is t h a t of i n se r tio n i n to C—H bo n ds.
T h u s “ : C H 2 ” re a cts wit h p rop a n e to give n -b u t a n e a n d isob u t a n e.

T h is re a ctio n is vir t u a lly u seless for sy n t h e tic p u r pose b u t ill u st r a tes t h e

ex t re m e re a ctivity of c a r be n e.

iii) A d ditio n to -bo n d.

C a r be n es u n de rgo cyclo a d d tio n wit h bo n d to give cyclop rop a n es.

e
 REACTION INTERMEDIATES 65

iv) Re a r r a n ge m e n t of c a r be n es
A l k ylc a r be n es c a n u n de rgo re a r r a n ge m e n t, wit h m igr a tio n of al k yl or h y d roge n . I n deed
t h ese re a r r a n ge m e n ts a re ge n e r a lly so r a pi d t h a t a d ditio n s to m u ltiple bo n ds a n d
i n se r tio n re a ctio n s, w h ic h a re so co m m o n for “ : C H 2 ”, a re sel do m e n co u n te re d wit h
a l k yl or di a l k yl c a r be n es. U n li k e re a r r a n ge m e n t of t h e species p revio u sly e n co u n te re d
i n t h is c h a p te r, m ost re a r r a n ge m e n ts of c a r be n es directly give st a ble m olec u les.

T h e re a r r a n ge m e n t of a cylc a r be n es to k e te n es is c a lle d t h e Wolff re a r r a n ge m e n t.

V. Nitrene
N it re n es a re n e u t r a l re a ctio n i n te r m e di a tes w h e re t h e ce n t r a l n it roge n a to m is elect ro n -
deficie n t a n d h a s a sex te t of elect ro n s.

Structure of nitrene
Li k e c a r be n es, n it re n es a lso m a y exist a s a si n gle t n it re n e w h e re t h e N- a to m is ‘ sp 2 ’
h y b ri dised. T wo of t h e t h ree h y b ri d or bit a ls a cco m m od a te t wo n o n -bo n de d elect ro n p a irs,
a n d t h e t h ir d h y b ri d or bit al is e ngaged i n a -bo n d for m a tio n . T h e u n h y b ri dise d p-or bit al
re m a i n s e m p ty. T h e s h a pe of s u c h n it re n es is pl a n a r. Nit re n es m a y a lso be for m e d a s a
t ri plet dir a dic a l i n w h ic h t h e N - a to m is sp- h y b ri dised. O n e of t h e t wo h y b rid or bit a ls
a cco m m od a tes a n o n -bo n de d elect ro n p a ir a n d t h e ot h e r h y b rid or bit a l is i n volved i n a
-bo n d for m a tio n . E a c h u n h y b ri dise d p -or bit a ls a cco m m od a tes a n elect ro n of p a r a llel spi n .
T h is i m p a r ts a dir a dica l n a t u re to t ri plet n it re n es t h a t a re li n e a r i n s h a pe.
66 REACTION INTERMEDIATES

Generation of Nitrene
Li k e c a r be n es, t h ese a re a lso ge n e r a ted by p h otoly tic, therm al or b a se-c a t a lysed
-eli m i n a tio n re a ctio n s.
Ex:

1)

2)

3)

4)

Fate of a Nitrenes
T h e re a ctio n s of n it re n es a re a lso si m il a r to t h ose of c a r be n es. A s i n t h a t c a se, m a n y
re a ctio n s i n w h ic h n itre n e i n te r m e di a tes a re s u spected p rob a bly do n ot i n volve free n it re n es.
It is ofte n ve ry diffic u lt to ob t a i n p roof i n a n y give n c a se t h a t a free n it re n e is or is n ot a n
i n te r m e di a te.

e
 REACTION INTERMEDIATES 67

i) D i m e ris a tio n of n it re n es.

ii) A d ditio n of n it re n e to do u ble bo n d.

iii) Re a r r a n ge m e n t of n it re n es.

1)

2) A cyl n it re n es u n de rgo s k elet a l re a r r a n ge m e n t to give a l k yl isocy a n a tes.

VI. Benzyne
T h ese a re t h e a ro m a tic re a ctio n i n te r m e di a tes h a vi n g a for m a l bo n d. T h e ge n e r a l n a m e

of t h e i n te r m e di a tes is a ry n e, a n d t h e st r u ct u re cor respo n di n g to t h e be n ze n e ri n g is c a lled

be n zy n e.

Structure of benzyne

Generation of benzyne
i) B e n zy n es a re ge n e r a ted b y t h e eli m i n a tio n of t wo or t h o gro u ps i n a be n ze n e ri ng.

Is
68 REACTION INTERMEDIATES

ii) I n sol u tio n p h a se, it c a n be ob t a i n e d fro m a b a se-i n d u ce d eli m i n a tio n of H C l fro m

c h lorobe n ze n e.

Mechanism

iii) E lect rolysis of p h t h a l a te.

Mechanism

iv) B e n ze n e di a zo n i u m -2-c a r box yl a te o n h e a ti n g deco m poses to for m be n zy n e.

ex
 REACTION INTERMEDIATES 69

Fate of benzyne
i) D i m e ris a tio n of be n zy n e.

ii) T ri m e ris a tio n of be n zy n e

B e n zy n e re a cts wit h many n u cleop h iles to for m diffe re n t cl a sses of orga n ic

co m po u n ds.

VII. Ion radicals

A n io n r a dic al is a re a ctio n i n te r m e di a te t h a t h a s a n u n p aire d elect ro n a n d h a s eit h e r a
positive c h a rge (c a tio n r a dic a l) or a n ega tive c h a rge (a n io n r a dic al).
Generation of anion radicals
K e to n es, a re n es, a n d n it ro co m po u n ds o n re d u ctio n wit h st ro n gly re d u ci ng m e t a ls li k e
sodi u m for m a n io n r a dic a ls.
Ex:

1)

2)

abcdab