325

STEREOCHEMISTRY
8.2 ISOMERISM
having same molccular
In organic chemistry we find numerous organic compounds
formula but differing in their physical and chemical propertics. Such compounds arc called
isomers and the property is known as isomerism.

8 As different compounds possess the same

physical and chemical
molecular formula, the difference in thcir

is attributed to different internal structures of

properties
below:
the molecules.

Therc are two main types of isomerism, as given

STEREOCHEMISTRY () Structural isomerism, and

(ii) Stereoisomerism

) Structural Isomerism: It is arrangement of atoms within the molecculc.

ducto different
Structural isomerism is fiurther divided into
(a) Chain isomerism
SYLLABUS (4 Lecturers) (b) Position isomerism

dimensional structures,
siructural isomeIS andstereoisomers, configuration (c) Functional isomerism
Representations of 3 actvity, absolute configuratiom
and synmetry and chirality,
cnantiomers, diastereomers, oplical (d) Mctamerism and
/somerisnm in transilional metal compounds
and conformational analysis (c) Tautomerism
(i) Stereoisomerism: It is due to different arrangcment of atoms around the carbon atom
in space. Stercoisomers have the same molecular as well as structural formulac but

8.1 INTRODUCTION
possess difterent spatial
arrangement of atoms in space, i.c configuration. It is also
known as spacc-isomerism. It is classificd as:

The Sereochemstry is the study of three dimensional configuration of the atoms (a) Geomctrical or Cis-trans isomerism,
that moke up a moleeules and the ways in which the arrangement affecis the physical and (b) Optical isomerism and
chemical properties of a molecule.
(c) Conformational isomerism
Onc of the major problems in organic chenmistry is to find out how the atons are arranged
Various types of isomerism have becn summarised below:
in molceules i.e. to determinc the structure
of organic compounds. Each different arrangement
of atoms corresponds to a different compound and each compound has its own characteristic
of chemical and
ISOMERISM
Set
physical properties. There is definitely a between the molccular
relationsihip
siructure
i.e. arrangement of atoms or groups of atoms in a molecule and its propertics.
Stnuctural isomerism Stcrco or Space isomcris1n
Compounds which have the same moleeular formula, but different structural formula (Stnictural isomers have
are calcd isomers and the (stereomers have tUhe same struclure
compounds having different configuration i.e. different reauv different stucture fornulace formula but differcnt configurations
posttion of aloms or groups in i.c. different arrangement of atoms i.c. different arrangement of atoms
called siereoIsomers. In other words, the
space are
That ave same atomic noc vithin the moleculec)
conncctivity, but different arrangement of their aroms in spaco, or groups
in space)
different configuration, are known as
slereoisomers and the study of stereoisoimers
properties is known as n
stereochemistry.
The prefix 'stereo' means al, 0
'threc-dimensio Chain or Position Functional Metamerism Tautomerism
stereochemistry is also known as 3D
Chemistry. Nuclear isomerism isomerism
In this chapter, we slhall isomerism
deal with different
of organic compounds types of structural as well as SLe Geometrical Optical Rotational
isomerism isomerism isomerism
(324)
 cONGEPTUAL ENGINEERING CHEMISTRY STEREOCHEMISTRY

isomerisms and aris es due to 1. It may be emphasiscd that

the different structures
of
tunctional
3 of conformational isomcrs of a
This is a special
case

atonm to
om
another ato m (oxygen or trogen) with the anCe are non superimposable on one
another but are casily
intercomverted into cach other
Tautomerism.

of a proton
from a
carbon

callcd
taulomers and the phen ation around single bonds. In conirast to this. the differcnt
(e) double bond structures of
supcTimposable over one another and at the same time opucai
migration and or
rcarraneement of single 1ctrical isomers are non

in cquilibrum
with each other g rcOnverted without breaking and making of bonds. Hence they cannot
tutomerism.

forms also
cNist
For able optical and isomersgeomctrical
Further. the
two
tautomeric

and less
stable
Isomer being in small amount,
also collcctively known as contigurational isomers. While confornnational isomers
isomer being in large
amount

tautomers of cach other. Acetaldchyde hoi exist only as mixture of different

a
conformational of a
forms, the configurational isomers
alcohol are
Smce one of the tc
o)
Acctaldehy de
and vinyl
amount as compared
to vinyt
alcohoI.
ist in individual substances. we shalt now discuss these
different ty pes of steTeo
is in large isomerism
stable isomer one by one.

(-C-) and the other, i.e., vinyl alcohol ontains

cane
8.4.1 Optical Isomerism
ie., acctaldchyde
contains a keto group
It has bcen observed that certain compounds rescmbie one another
in their chemical
tautomerism 1s also called keto-en.
ot as well as in most their
an enolic group (=C-OH).
this type nroperties ot phy sicai
properties but they differ in their behaviour
towa the action of plane polarised light Such compounds are calied
tautomerism. opsically active a2d
H H this phenomenon is called optical activity Compounds, which rotate the pianc
polarised ight
CH-C =0 H-C =-0-H towards the right are said to be dextro-rotatory and are representod as d or (-) form, where as
those which rotate it to the left are called laevo-rotatory represented as
i

or (-) form These

keto enol tautomerism; keto form being mai.
major
Similarly, acetoacetic ester also shows isomers are said to show optical isomerism. Before proceeding further. it is
(i)
minor product important to
cnolic form being understand the terms polarised light and optical activity
product and
OH
O Polarised Light: An ordinary ray of light consists of ciectromagnetuc waves and its
CH-C-CH,-COOC,H, CH,-C= CH-COoc,H, vibrations taking place in all planes perpendicular to the direction in which it travcis
(cnolic form) Monochromatic light, on the other hand, consists of waves of one wave iength. Even sucha
(keto form)
ray has its vibrations in all the planes.
methane are tautomers
ii) Normal and Aci-forms of nitro 0-H However, if a ray of monochromatic light is passed through a Nicol prism, the wavc
motion of cmergent light is restricted to only one plane. Such a beam af light which has vibration
H-C=N
-
o only in one plane is called plane polarized light or unidirectional light. The Nicoi prism used to
obtain plane polarized light is called a polar1zer (Fig. 8.1).
(Normal Form) (Aci Fornm)
The compounds showing tautomerism give reactions of the functional groups present in OR
each tautomer i.e. reactions of both the functional group. The two tautomers can be separated
by special methods and can be kept in separate fornms only under special conditions. Under Ordinary Nicol Plane An Optically (Polarised Light)
ordinary conditions tautomers exist in cquilibrium with each other. Light Prism Polarised Actine Plan Plane
Light Substace Rotatcd Rotared
Tow ards Towards
8.4 STEREOisOMERISM Right Let

The isomerism which

arises due to difference in the arrangement of atoms in space Fig.8.1 Polarization of light
ts The isomers which have the same
called stereoisomerism. structure but difierent molecular Optical Activity: When the plane polarized lght is allowed to fall oa another Nicol
relative arrangements of atoms or
groups in space i.c different configuration are
stercoisomers and the phenomenon is called stereoisomerism. There are three types o caliea prism with its axis parallel to the first Nicol prism, the plane polarized light passes thought it
stereoisomerism: withoutundergoing any deviation. The first Nicol prism is known as polartzer and the second
Nicol prism is known as analyzer. If the axis of analyzer is kept at right angle to polarizer.
(a) Optical isomerisms (6) Geometrical isomerism (c) Conformational isomerism. Omplcte darkness appears due to total internal reflection (Fig 8
2)
 cONCEPTUAL ENGEERING CHEMIS
TRY
STEREOCHEMISTRY

8.5 CONCEPT OF CHIRALITY 331

HPN Optically Second

Eyc Chiral structures
A structure or
rst
Activc Nicol Prism object is said to be chiral (or
Liglit Nicol Prisnm
Substance (Analyser) symmetry and is not superimposable on its mirror
disynmmetric) if it has no plane of
Souce
(Polariser) chiral object is human hand. lt docs not have any plane ofimage. The most perfect examplc of a
lines indicate the angle of rotationi symmetry and cannot be
upto a mirror, the image looks like a superimposcd
of polarimeter (the dotted on its mirror image. If you hold your left hand
Fig. 8.2 Representation
and analyzer with their axis pcrpendicular to cach othe if vou try to superimpose one hand over the
other (both palms down), right hand but
The arrangement of polarizer you can not do it
of solutions organic compound towards plane polarized
of lioht 8.3). Similarly right handed glove and a left handed
a
glove are chiral objects
(Fig
is used to study the behaviour The term chiral based upon the Greck
For this purpose a polarimeter
tube containing solulion or organic compound is placed betwcen word cheir
the two If some
Nicol prisms. light appears, it indicates that organic compound has rotated introduccd by Cah1n, Ingold and Prelog in 1964. Thus chirality(which means hand) was first
means 'handedness' i.c.. the
plane polarized light through a cortain angle. Such compounds
which can rotate the plane rclationship which cxists between the left and right hands. In recent
and chiralty have almost ycars, the terms chiral
polarized light through a certain angle
are known as oplically active compounds. The completely replaced the old terms
disymmetric and
property by virtue of which the orgamic compounds can otate the plane polarized lkght is respectivecly. disymmelry
known as optical activity. Many organic molecules such as lactic acid
CH CHCICH,CH3) represent [CH,CH(OH)CO0H|
chiral structures. The substances
and 2-chlorobutane
8.4.2 Specific Rotation are said to having chiral structures
possess the property of chirality and these substances are
The angle through which plane polarized light is rotatcd by an optically active compound active. optically
is known as angle of rotation. It can be represented by alpha (a) and it can be determincd
with the help of an instrument called Polarimeter.
The angle of rotation depends upon the following factors:
i) Naturc of the compound (i) Nature of Solvent
(ii) Concentration of solution (iv) Wavelength of light used
(v) Length of the solution column through which the light passes
(vi) Temperature
The rotatory power of a given solution is usually expressed as specific rotation, which No plan of Object Image
Canbe defincd as the angle of rotation (a) produced by one decimetre length of solution Symnctry Non-Sunperimposable.
having one gram of the substance per militre. The measurement of rotation is carricd out at Fig. 8.3 Chiral structure
temperature T using sodium light (the D lincs).
Achiral structures
Specific rotation= - 100xobserved angle of rotation 0
A structure or
object which has Miror
Length of decimetersegrams
x of substances present aplane of symmetry and
in 100 ml of solution superimposable on its mirror image is
or

The
in degree at T°
specific
h 00xo
lal=C
rotation of a
compound is written as la = xo where X° is the rotation
known as achiral (or
symmetrical). A
planc of symmetry is a planc, real or A
Dottcd line represents
imaginary, which divides a structure or an plane of syimmetry
ATA
Object
Superimposable
Image

tenmperature. For example, [«= -20° mecans that a objcct into two cqual halves so that one
is obtained at 20°C of specific rotation of - Fig. 8.4 Achiral structure
tempcrature and using wavclength of sodium line (5893A). Molecular half is the mirror
image of the other halt.
rotation is the product of specific rotation and
molecular mass. rOr example, the letter structures. It can be easily seen that each of these
A represents achiral
p l a n e ofsymmetry and is superimposable on its nirror image (Fig. 8.4).
 cONCEPTUAL ENGINEERINGCHEMISTRY STEREOCHEMISTRY

333
thosc of
methane carbon
and carbon tetrachlorid
tetrach
It must be cmphasizcd,
332
molccules such as are however, that certain molccules
Similarly, many tuieal ccntre and still they may be achiral
or may-contain more than onc
s m m e t r i c a l in n a t u r e .
il when placcd upon the otho one
LCHCI-CHC-CH3. which has
non-dissymmctric. For instance, 2,3-dichlorobutanc,
two
be supermposable chiral centres (those
Two objccts are said to
that are like mirror images of ead cameric
forms one of which is not chiral marked*) exists in many
on cach
other. Two objects becausc it has a plane of
For cxample, two note booe.
lie symmetry as shown below.
corresponding parts non-superimposable.
or
cither superimposable
may be are superimposable. CH
relationship
same having mirror image
size

compounds
Chirality in organic the presence of at leact
Plane of
are chiral in nature due to
***

Most of the organic compounds ne syninetry

chiral carbon or chiral centre in the molecule. Previously a chiral carbon atom was ferred
carbon or chiral centre is a carbon atom which ishou H -C -C1
toasymmetric carbon. A chiral
1ofour diferent monovalent atoms
or groups such as Cabed There can bc two diferen
tetrahedral models for Cabod which differ in the spatial arrangcments ot various groups attached

to carbon as shown in Fig. 8.5 On the other hand, havc certain molecules that are chiral even
we
Mirror
though they do not
contain any chiral carbon. Allenes (RCH C CHR) represent a well known class of such
= =

compounds as illustrated below.

H H
C =C=

H3C CH3 H3C CH3

d Fig.8.7 Non- superimposable mirror image of 2, 3-pentadiene

It may be scen by molccular models that chirality in 2,
Fig. 8.5 Non-superimposable mirror image models of chiral C atom. 3-pentadiene arises duc to the
fact that the two groups singly bound to one of the end carbon atoms of allene
system are in a
Each of the two models is related to the other like an object to its mirror image and one dhfferent plane than the two groups singly bound to the other end carbon of the allene
systcm.
cannot be superimposed on the other. Each of these models, therefore, represents a chiral
8.6 TYPES OF OPTICAL
structure. ISOMERS
Similarly we can have two non-superimposable mirror image structures for any It has been observed that optically active compounds alway's exist in two or more

containing a chiral carbon or chiral centre. For example, lactic acid isomeric fornms, which differ with rospcct to their optical activity. As alcady stated, the isomers
known compound
CHCH(OHCOOH] is a chiral molecule since it contains a chiral carbon marked as () which resemble one another in their chemical reactions and most of the physical properties but
Pig. 8.6]. differ in their behaviour towards polarised light are called optical isomers and the phenomenon
is known as optical isomerism.
Mirror
Mirror COOH There are two main types of optical isomerism. These are
COOH
COOH COOH )Enantiomerism (ii) Diastereomerism.
-H
H-C-OH HO-C-H OH HO 8.6.1 Enantiomerism
CH3 CH3 In 1948, Pasteur observed that an aqucous solution of sodium ammonium tartarate was
CH3 CH found to be optically active. He separated two distinct type of crystals from the solution of this.
(a) Planar structure
(b) Tetrahcdral structure compound and found that cach of erystal possessed optical activity equal in magnitude but
oPposite in its sign. The shape of the two typcs of crystals was found to diffèrent and they were
Fig. 8.6.
Nonsuperimposable mirror images: Lactic acid
non-superimposable.
 STEREOCHEMISTRY

336
cONCEPTUAL ENGINEERING MISTRY
1-butanol |C2H, "CH{CH,CH,OH]
contain one chiral carbon cach (thc onc markcd")
mirror thercfore exist as cnantiomeric forms as shown alrcady On the other hand. there can be
are
non-superimposablc

ima S of
structures
dir
but in opposite
alecules such as 2. 3-pentadicne which
molecular

Such
isomers
whose
plane-polariscd light equally tions are do not contain
any chisal carbon but they still possess
rotate the of object and its miror-i
ir
image of rality and thus exhibit enantiomerism
and which 1 he phenomcnon
the property
cach other enantiomorphs.
nirror-image isomers differ
enantiomers or
Since theobjcct and its mirror- only It may be concluded, therefore, the ch1rality (i.c.,
the property of cxisting
Anoun as enantiomerism.
of stcreoic
as
non
15omerism is called
of atoms,
cnantiomerism is
only a particular type ISm. Superimposable mirtor images) Is the furdamental and only condition of enontiomerism

the spatal arrangcment 15omers was justified by Van't H o on

.
in
its mirror-image
The existence of object andcarbon atom.
Tetrahedral models of an imaginary compotnd
Characteristics of Enantiomers
of
tetrahedral
of concept
tartaric acid will be shown in next atict important characteristics of the cnantiomers of a
the hasis
has alrecady becn
shown and that of The given substance are described bclow
ofthe type Cahed
two enantiomcrs
of the compound. They have identical physical properties such as melting points, boiling points. densitics,
These models represent
enantiomcric forms of [CH,CH(OH)COOHI
Similarly, we can
construct modcls of
cxhihie
solubilities. rcfractive indices.
The only diference lies in the direction on of rotation of
[C,H,CH(CH,)CH,OH|,(Fig. 8.8), which is also known to plane polarised light, although the magnitude of specifie rotation is the samo
and2-mcthyl-1-butanol
enantiomerism. (u) They have identical chemical propertiex except in reactions ivith other optically active
Mirror compounds. For example, the ordnary chemical reactions of (+) lactice acid are exactly
hkc thosc of (-) lactic acid. Thore may be a differenee, however, in the rates of reactions
CH at which two enantioncrs react with some other optically active compound. For instancc
H the rate of esterification of (+) lactic acid with (+) sec. butyl alcohol
H-
CH,OH HOH,C
CHCH,CH(OH)CH,1 would be different from the rate of esterification of(-) lactic
acid with the same alcohol.
CH (ui) They have different biological properties, In contrast to plhysical and usuaB chenmical
CH propertics, enantiomcrs are quitc different in their biological propcrties. For cxample.
Fig.8.8. Enantiomeric forms of 2-methyl-1-butanol. (+) sugar plays an important role in animal metabolism whercas (-) sugar is not
We find that it is possible to construct two models which are non-superimposable mirror metabolized at all. Similarly. (+) tartaric acid is readily consumcd by the mould penicillium
glaucum while (-) tartaric acid is not,
images of cach other and as such they represent the different enantiomers.
(iv) When equal quantities of enantiomers are mixed together it results in the formation
It may be pointed Mirror Cl
out, however, that the of an optically called racemic modilication or racemic misture or
inactive form
racemate. The raccmic modification is distinguished by using the prefix (+) bcfore the
molccules of most of the
-H name of the compound. For example, if cqual quantities of (+) lactic acid and (-) lactic
compounds containing a H-
acid are mixed with cach other, we get racemic or (+) lactic acid which is optically
tetrahedral carbon atom are
inactive.
superimposable on their
mirror images as illustrated Br Br 8.7 PLANAR REPRESENTATION OF THREE DIMENSIONAL
with of models of bromochloromethane FORMULAE: (FISCHER PROJECTION FORMULAE)
below the help CH,CIBr. Such compounds do not exhibit
cnantiomerism becausce all their molecules are of the same
type. lt is not very convenient to represent the formulac of sterco-compounds on paper. A
Essential Condition for Enantiomerism Simplc, method was introduced by Enmil Fischer (1891) for projccting threc dimensional formulac
of chiral molecules on planar surfacc. The planar representations are called Fischer projection
Enantiomeric molecules are always
The
non-superimposable mirror images of each other formulae.
non-superimposability of mirror images
invariably arises due to chiral nature of the formulac:
molecules. Now, a molecule is termed as
chiral if it has no plane of The followving proccdure is adopted for writing the projection
therefore. non-superimposable on ils mirror image. symmetry and 1s, attached to cbiraB
) The chiral molccule is considercd to be so hcld that two groups
the obscrver whilc the other two groups lie
Chirality in most of the enantiomeric molecules is itsclf due to the carbon lic horizontally and point towards
one chiral carbon in the
molecule. For example, lactic acid presence of at least vertically and point away from thc observer.
[CH*CH(OH)COOH]
and 2-
 cONCEPTUAL ENGINEERING CHEMISTRY
STEREOCHEMISTRY
chiral carbon are then projected to tlthe
The various groups
attached to the
bonds poming tovards the observer
plane of the (vIf positions of twO groups or
horizontallncs represent atoms about the ral
so that
anes
paperrepresent bonds pomting avway from the observer. In case the chiraltica
moloc to
inversion of contiguration But carbon are interch
337
remains unaltered if we carry out two such hanged it also lead
containswo or more chiral
carbons, cach carbon is considered separatel as ddescribcdle
tely ne interchanges, theconfiguralon
above ÇOOH
i The vertical part of the projection formula should represent, so far as possible, th
longest chain of carbon atoms in the molecuie win the carbon atom to be numbered First ÇOOH
H- OH COOH
I according to IUPAC system beng written at the top. Second
HO-
Interclhange
For instance the prajection formulhe ot the two enantiomers of lactie acid ma . HO-
epresented as shown below.
bc CH, Intercltange -CH
CH,
CoOH COOH VLactic acid H
VI(+) Latic acid
H-COH Inversion of configuration Vit(- Lanc acid
HO-C-H Configuration samc as
that of 1
CH CH It is quite cvident from above that one
interchange is
(R)- Lactie Acid S)- Lactic Acid 270 while two interchanges are
cquivalent to rotation by 180 cquivalent to rotation by 90° or

(iv) Very often the chiral carbon atom is not written at all whilc
writing the
formulac. It is taken for granted that the chiral carbon is located where the lines showing
projection A7.1 Diastereomerism: Compounds having more than one chiral carbon
the horizontal and vertical bonds cross as shown below. We have learnt that a compound
containing onc chiral centre evist
forms which are known as enantiomers of cach in two stercoisomeric
other. But
COOH onc chiral centre can exist in more than two compounds
contaming more than
stercosomeric forms. To illustrate this
HO -H Ict us consider the case of 2, statement
3-dichloropcntanc:
C CH CH-CH- CH-CH-CH,
(v) lfnecessary planar formula may be imagined to be rotated from end to end but
wthout liftung i from the plane of the
paper. Rotation by 180° in the plane of the
paper docs not bring about any change of which contains two chiral ccntres. Since the four
configuration.
For examplc: chiral centre are not the samc as those attached to the
different groups attachod to onc
other. the two chiral carbon atoms are
COOH COOH dissimilar from onc another. There are as
many as four stereoisomers (I, 11. Il and iV) possthBc
Rotation for this compound.
H-OH Throughh 180°
HO -H

CH3 CH CH3 CH3 CH3

I-) Latúc acid
CH
Il(-)Laticacid H- C
(No change in configuration: I and II represent the
C H- -H
compound) same
But rotation by 90° or 270° lecads to inversion of
configuration (i.e., changes one CI -H -0 H-C -CI Cl
configuration into its mirror imagc) so that the new configuration represents the
enantiomcr of the original compound. C2H C2H5 CzH5 Ciis

COOH H
Rotation One pair of enantioiners SCcond pair of enaniiomers
H -OH CH -COOH
Through 90 EXamination of formulae I and II reveals that thcy are non-superimposable mirror
CH OH IV are also
gs cach other and hence represent a pair of enantiomers Similarly. Ill and
IIl-Lacticacid IVELactic acid o
upTimposable mirror images of cach other andas such represent another pair ot cnntiomers.
(nversion of contiguration)
 STEREOCHEMISTRY

cONCEPTUAL ENGINEERING CHEMISTTRY

of Enantiomere.
Comparison and Diastered
III
formula I with fornula
the Enantiomers
Let us now
conmpare
CH3
CH3 Same These stcrcoisomcrsS have a miror magc
Diastercomcrs
Conliguration C1
-0 relationship
H smage rolauonsisp
These hav e Similar ply sical propcries. such as2 i tesc
H- -CI melting point. boiling point. sohubriity in a tac ditcrent
physcal
CI Mirror Image
Configuration given solvent, density ctc smcng po. btung pcixtprperties sh
soluuaty in3
C2H5 3. These cannot be separated by such methods
3 Thesc ca be
parad cu
immediatcly clear that the two tormulac have i1dentical configurations abot adsurptcn caDmEoSu
It becomes
(C-) but mirror image configurations about the
other
chiral carbon (C3) Th 4 Tha hac optical rotation opposte
onc chiral carbon They may bne opticai mtaion a
forms are ncither 1dentical nor mirror images of cach other. Such
direction but lothe same cxient the same er
nct result is that thhe two OPpose drecuns b o a ticremt e i
ereoisomers of a suhs tance which are not mirror images of cach other are known as They have identical chcmical properics
diastercomers. In addition to formulac I and 11, formulae I and lIN, II and I , II and IV also cxcept with other optically activ c compounds
Thave rdcatical ccmcal propats tet
diker he rae of
xtons vpbN
represent pairs of diastercomcrs
3-Chloro-2-butanol affords another cvample of a compound having 2 dissimilar chiral
8.8 MESO COMPOUNDS
carbon atoms and can evist in four stercoisomeric forms as given bclow:
Let us now consider a compound
containing tso simiiar chiral cestres eha
CH3 CH3 CH3 CH3 the same set of four different groups aitached to cach of
th ceral a:bon atcms ANiai
sample of such a compound is provided by tartarie acid.
H- -OH HO -OH HO- H
CHOHC00H
Cl- -H -CI H -CI Cl-C H
CHOHC00H
CH3 CH3 CH3 CH3 In view of the fact that it has two chiral centres one may evpoct tbe eistue of fur
VI VII VIII
stercoisomers of this acid having the configurations iN X. XI and X
It may be scon
thait structures V and VII, V and VII. VI and VII: VI and VIll represent COOH COOH cOOH
pairs of diasterconers.
-OH HO-
Characteristics of diastereomers:
The important characteristics of diastereomers are HO H -0H -OH
as
follows
i) They show similar, but non identical, chemical properties. In the reactions of two
diastercomers with a given reagent, the rates of reactions are
cOOH coOH
generally different. X
() They have different phy sical properties.
such as melting points. boiling points, densities. Sauperinpesabie misror na~s
solubilities. refractive indices. Even specific rotations are different: this docs not, or Pair of enantioniers
represet 2uty ane compond
course. appiy to diasterconiers which are
geometrical isomers since such diastereomers
arc not optically active rormulae IX and X are non-superinmposable miror images ofeach other and. theretore.

Cpresent a pair of optically active enantiomers

H1) On account of difterences phy sical properties. they can be rather casily separatca
in
Close evaminaticn ct
rormulae XI and XII again have a mimor image relatioeship
through fractional cry stalhzatio. fractional distillation. on the otner
chromatography ete u l a c , however. shows that one ofthese stuetures m2y be superimpased
 sTEREOCHEMISTRY 341
GONGEPTUAL ENGNEERNG CHEMS TRY
-
External Compensation
These two
formulan
uslac. therefore
the pianc ed
the fpapcr
compound. Furih
In a raccmK mixhure cqusmoiar mxture of two enantiomsers. say (t) and f- lacte
through 180
w:thm
molecutcs of the
same rth er
rotating
it
mirrer mage
are prescnt
Chis are prescnt The molecules of onc cnantiomer woutd be preseat m a quantaty cquaito
Bat sabBe
that in spite This mcans that rotation of planc polarised ltght by cach
other enantomer.
oth
eiIla
37 for A) reel
chiral COOH those
o t the 1somc
crTAUYR

. 7he
moiccule is mot
and
dbe cqual magnitude opposite in sigt e dirction Thereforc, exact conceliotion
in
ntre 2 o n e half
of its
ren chira
because t has a plane of symmetry,
As such thc
l rotstion would take place and the cqumolar mixture would be opttcally inactve The
Thas is thc other half ollatton t rolatio of
one enantiomer
by the other m an cquimolar mixture of the
mirror mage of Plane of
bcmg is optically
formula XI (or Ai)
mslecule
by is known as
exteraalcompensation and the racemte iaxiure it sald to be
compound
rcpresentod whose Syinmctr eantiomers
compound
inzctne Srch
an epiicalily
acTIve

cnntain wo
H -OH externally compensaled

éven fhongh tey

olecnies 2* mar chiral
compound.
It may be pointcd out that if the two cnantiomers are not nuvcd in cqumolar quartities
mCso
k n u n as a
c e n t r e s is
fnt morei
chirl
compounds arc
COOH
thc rotation
caused by one enanttomet is not evactly cancelled by the other As such this misture
the molecules of such
cxpland above The ducction of rotatton corresponds to that of the enantiomcr
stll cxhib:ts sommc optically activity
As
supermposable on their mirror images
(-) fartaric octd (tormula IX). (+) tartaric otescnt 10 quantity but the spec1tic rotation is lesser In this way partal conpensatioa
larger
Thus, tartaric acid custs in three forms mnture focd is said to be partially racemised.
lartaric actd (formula XI
or XIl) Lkes place and the
ccud ifarnula A) and eso

acid represents a diastcreomer of t-

Although optically inactive. the meso-tartariC ot
Comparison of External and Internal Componsations
)tartanic acid Iuternal Compensation
Eternal Compcnsation
are pcrmancntly inactive and arc said to be
it should be noted that meso compounds This is due to tihc nor-image relationstup
molcculc cancels the cffcet of other half This sduc to thc murrot-imagc tciationsh1p
is
internally compensated ie onc half of the bctwech the uructurcs of the molccules of
the stnuctures of two halves of tie sane
| betwcen
wo cnzntiotners muved togcthcr, in cqual nolcculc
Number of possible stereoisomers in compounds containing different
number of chiral centres this ca5e o11e alf of the molecule
In 1his case the molccules of onc enautioner In
It may be stated that the maximum possible number of stercoisomers of a molecule is
canccl the rotatson of the other eantiomer
couiter-bilances thie rotation of the other half

when n is the number the molecule. Thus the molecules having 1.2 and
of chiral centres in
internally compensted compound or Meso forn
2" The ricenmate formed is a mirhrc of two
3 chiral carbon atoms evist in respectively The number is, of
2, 4 and 8 stereoisomeric forms tsomer conpounds
represcuts a siugle pure compoud
course. less than the maximum if some of the isomers exist in meso forn intemal compensation is not possible.
Complcte ot partal exteral compcusation of Partial
totation S possible
8.8.1 internal and External Compensation
effect aund it not pOssible to is
It is a rcversible process and the racemic It is a permancnt
and resolve an intcrnally compensated molecule iuto
Internal Compensation mixture can be resoBved into () (-|
opticaly active forus
it has becn stated above that meso compounds are optically inactive because their enantiomers
molecules are not chiral even although they contain two (or more) chiral centres For example, OFRAND S NOTATIONS
it is clear from the structural formula of meso-tartaric acid that the top half of the structure is
8.9 CONFIGURATION ON THE BASIS
specify a particular
Prelog suggested a very simple procedure
to
the mirror image of the bottom half. As such the optical Cahn, Ingold and
from Sinister
Contiguration in terms of prefixcs R or S.
The letter R is taken from Rectus and S
activity doe to onc chiral centre is counterbalanced by the COOH
The procedure involves the following two steps:
optical activity duc to the other and the compound is optically assignied a
the chiral cen1re are
inactivc The compensation of optical activity duc to one - -OH Step 1. The four atoms or groups of atoms bonded to
of rules known as sequence rules
half of a molecule by the other half is known as internal accordance with a set
Planc of . sequence of priorities in

compensation and the molccule is said to be internully Symmctry Sequence rules.

campensated. An ntcrnally compensatcd moiccule is -OH
The sequence rules are as follows
attached to the chiral centre are differen: from
one
permaneatly inactive
COOH ) a l l the four atoms irectly number The atom of highest
1s determined by
atomic
another, sequence of priortties
 cONCEPTUAL ENGINEERIN
ING CHEMISTRY
the lowest
whilc the one with
lowest atom STEREOCHEMISTRY

nunmber gets the highest prnority

atomic
comes last in order
of priority. For example, in the compoundind 1-bromo-1-chl
1-chloro-cthane, number
of will be Br, CI, C, H.
CH,CH(CI) Br, the sequencc priorities H 343
i) Iftwo or more atoms dircctly attached to the chiral centre have the same tomic n
the relative priorities may be
fixed by comparing the next atoms in the oro mber, H-C
ups f Cven
this does not solve the problem, the comparison may be extended to to the next atom H
so on. For cxample, in sec-butyl alcohol, and H-C
H,C-HC- -CH3 As such the atoms next to the carbon
OH
Sten 2. After deciding the attached to chiral centre are
the relative priorities of CH, and CHs are decided as follows. Each scquence of pnorities, treated as C. C and C
of these prou where the the molecule is
prIOrity is directed away fromimagincd
groupof lowest to be in a
linkcd to the chiral centre through the same atom, 1.., carbon. The ps position
are H, H and H while in
C,H; they are C, H and H. Since
next atoms in
carbon has a higher
CH. arrangemcnt of remaining groups in
us Now, we
decreasing order of their priorities If inlook at the
atomis the eye travels in clockwise
number than hydrogen, CH; gcts higher direction, the doing so,
priority. right). If, on the other hand, the eye travelsconfiguration is specified as R
in anticlockwise (Latin. rectus=
Gii) Ifa group has an atom X linked to some other atom by double or is specified as S (Latin: sinister direction. the configuration
considered equivalent to two or three such atoms. tor
triple bond, X is
=

left)
instancCe, if we compare the Let illustrate the above rules by
us

Lactic
considering some speciic examples
groups, -C =0 and () acid, CH,CH(OH)COOH.
-CH,OH, the former gets higher priority as the next atoms in it
The sequence of
are
cquivalent to 0, 0, H while in CH,OH they are 0, H, H. priorities is OH. COOH, CH, H. Therefore, the specific
may be designated as: configuration
It may be noted, however, that if in a
group two or three atoms of X (are separately
linked to some atom through
single bonds, such a group would get priority over the group ÇOOH COOH
containing doubly or triply bonded X. For example, let us compare the groups - CH, and
CH
=

CH-CH In both these

groups, the next atoms will be taken as C, C, H. However, in
CH Ho
CH3
H
-CH-CH, the two carbons are
actually attached through single bonds while in -C
R
CH, Gi) Chloroiodomethane sulphonie acid,
CH{CI)S,OH
=

there is
CH The
sequence of priorities is I, CI, SO,H and H. Therefore, R and S configurations
only one carbon attached
through double bond. As such the may be represent as shown below.
H group -CH-CH, get
Clockwise Anti-Clockwis
priority over -

C =CH,

Similarly Cqgiy-io gets priority over -CH =

CH- which in turn gets
priority over -CH CH =

Note. The
phenyl group is considered as if it has one of Kekule
that is structures
So,H SO H

R
 STEREOCHEMISTRY
345
cONCEPTUAL
ENGINEERING EMISTRY ae Dimensional Representation
Three
CONFIGURATION

CHO CHO
SPECIFICATION
OF t
acid are I and II shown
8.10 enantiomers
of lactic ow. One
two
configurations ofthe acid rile the other represents lacvo or H -OH HO- -H
The dextro or (+)
represents
configurations

ofthese
lactic acid.
COOH CH,OH CHOH
COOH
HO H
H-OH
CHs CH3 Reasons for selecting glyceraldehyde as the standard
Glyceraldehyde was chosen on the standard mainly because of the following reasons:

which onc of the two cnantiomers, (+) or(-). has. () It is the simplest carbohydrate-an aldotriose its configuration could be casily related to
Specification of configuration
means
those of the other important carbohydrates.
I1. In other words we do not know tho
the configuration I and which has the configuration
c) Since glyceraldehyde contains very reactive functional groups it could be converted
absolute configuration of cach of the two enantiomers.
into many other types of compounds. In this way it could be configurationally related to
actual or

In the carlier days, it possible to determine the absolute configurations of the

was not a large number of compounds.
to know the absolute configuration of an
compounds. Fortunately, it is not always necessary
we are more interested in knowing the relative Correlation of configuration
optically active compound. On the other hand,
when an optically active compound then relative configurations by relating their
configurations of different compounds. For examplc, Many othcr compounds were assigned
in whether the configurations of the either the compound under
undergoes a chemical reaction, we are mainly
interested
configuration to that of D- or L glyccraldehyde For this purpose
in their actual configurations. it is converted into the given compound
reactant and its product are same or different and not Cxamination is converted into D- or L glyceraldehyde or
The
by means of rcactions which do breaking of bonds to a chiral centre.
not involve

(A) Relative configurations by D and L Notation is that ifa reaction

general principle involved in correlating the configurations of two compounds about that chiral
docs not involve the breaking of a bond about a chiral centre,
the configuration
It was proposed by Emil Fischer (1885) that a standard reference compound should
examples of the correlations of the conf+gurations
be chosen to assign relative configurations to various optically active compounds. The compound centre remains unchangcd. Some important
chosen as the standard was glyceraldenyde (CH,OHCHOHCHO) and its two cnantiomers arc given below:
acid can be obtained by the oxidation
were designated by the symbols D and L. It must be made clear that the symbol D and L refer i) Configuration of(-)Glyeerie Acid: Glyceric(-)
this reaction does not involve breaking
to configuration and are quite different from the prefixes d and 1(read as "dextro" and "lacvo") of D(+)-glyceraldehyde as shown below. Since
acid must have the same contiguration as
which refer to the direction of rotation. (+)-Glyceraldchyde was arbitrarily assigned the of bonds about the chiral centre, (-)-glyceric
that of glyceraldehyde taken i.c. D configuration.
configuration IlI (in which the -OH group attached to chiral carbon is towards right) and was
giventhe symbol D. The (-) enantiomer was assigned the configuration IV (in which the-OH CHO COOH
group attached to chiral carbon is towards left) and was given the symbol L.
H-C-OH
Oxid H- -OH
Planar Representation (Br,/HO)
CHOH
CH,OH D4-Glyceric acid
CHO CHO D4+Glyccraldehyde

H-C-OH HO-C-H Acid: The configuration of (+)

lactic acid was established
i) Configuration of (+) Lactic
CH2OH CH2OH of L-(-)-glyceraldehyde by
to be similar to that
the following reactions:

IV
D-(+)-Glyceraldehyde L-)-Glyceraldclyde
 STEREOCHEMISTRY

cONCEPTUAL ENGINEERING ISTRY 47

SngeD--) tartarnc acd
assngnod configuratioa
was
narurall bave the mirrot image configurationie VIl VI L1 Lartanc acid wouid
COOH
CHO PBr-PBr
-OH COOH
--OH HO-
(BHO -H
CHOH
CHOH -OH
D4Cituncaid
H- -OH HO-
CHO COOH
COOH
HO
Redeci H0- -H
V
COOH
-H Br VII
CHBr CH D4--Tartanc acid L4+-Tartarnie acid
L4atic acid
-- It must be emplias1zed that there Is no direct
2 - d p r p acd relationship betwcen absolutc configuration
and dirccton of rotation of poiarisd ight. lwo substances may have similar relative
configuratons
i Configuration of CHO and vct may rotate the plane ot light m ditterent darcctions For example,
D-(-)-gly ceraldchy de
Tartaric Acid: When and D-(-)-glyccric acid have similar
contiguration even though the former is dextrorotatory
D-(+-glyceraldchyde H-C-OH while the latter is levorotatory
was converted into
CHOH CHO
COOH
tartaric acid by the
series of reactions D-+-Glyocraldchyde -C-OH
Two configuratioms pessble aroumd H-C-OH
shown bclow, a mixture HCN ncw chiral centre markod"
of two products was CHOH CHOH
DGlraldhvd D4Glyricacid
obtaincd These two
CN N
products d1iffercd fromn Similarly two compounds may have different configurations and
H-¢-OH HO even then they may
cach other in ther the plane of light in the samc dirction. For example,
configuration around
rotate
D-(+)-glyceraldehyde and L-()
H- -OH H -OH actic acid havc oppositc configurations but the samc sign of rotation
newly creatcd chiral
CHO COOH
centre (marked "). One CH2OH CH2OH
of the products was the H-C-0H HO- -H
1nactive or mesotartaric
Hydrolysisl Ba(OH) Hydrolysis Ba(OH)
acid (V). The other was COOH COOH CHOH CH-OH
the optically actiVe DGlycecraldcisyde LLactio acid

tartaric acid which -C"- -OH HO-

rotatcd the plane of light
H-C-OH -OH
(B)Absolute configuration
tothe Icft i.c. it was(- Bijvoer (1951) was able to determine the absolute configuration of a compound
-tartaric acid. Since it CH2OH H2OH by using X-ray diffraction studies. The acual arrangement in space of the atoms or
was obtained from
D Oxid. (HNO) Oxid (HNo) groups constituting a particular siereoisomer is called absoute The first
glyceraldchyde by configuration
rcactions which did not COOH compound whose absolute configuration was determincd was sodium rubidium salt of (t)-
COOH tartaric acid. Bijvoct confimed that (+-tartaric acid actualy has the same configuration, which
involve breaking of
bonds around the
-C" OH HO- -H was previously assumed to have on the basis of configurational relationship between
original chiral centre, it H-C-OH glvceraldchyde and tartaric acid (as described carlicr). If the assumed configuration of (
H -OH
artaric acid was correct, the assumcd configuration of the two enantiomers of glyceraldehyde
was assigned D-
COOH COOH
configuration i.c. the u s t also be correct. As such tlhe configuration of all other compounds derived by corrclation
same as that of starting VI
IICso-Tartaric acid
glyceraldchyde. D-(--Tartario acid
 cONCEPTuAL ENGINEERING CHEMIS $TEREOCHEMISTRY

TRY
the
rolative confi ration assgned
hus of prionties C
graidoksdes
mut de eorret
aid
ocs

tdecussed
eartisr) rbohydrates
carbohys and a large mumber of The soquence
is
-.CH-CH,, H Tberefore. coefig
w ad Ha their
sthsoBute
configuratoe

rogwvs

xnds
actualh
Snnle but roochemically important compounds
steroochemrcally imporant
First
aher
coetiguratioms of so H Second
Taete
Interchange
bekm n the planar
im

CHO (1) H OH HO -H nterchag

a
-CHCH
HO H,CH CHCH
CHOH
CHOR L-Hibralkichyde The sequence of priorities OH.
is
CH,CH3. CH. H
Therefore. cofiguratacm n
5

COOR COOH CHO First CHO Seoond CHO

HO- f-H Interchang Interchan
(n1) CH CH -NH -

CH-OH CHOH
Llatic id NH
The scqucnce of prioritics is NH,. CHO, CH3. H Therefore, comfiguratsom 3

cOOH cOOH
H -OH 8.10.2 Configuration of Compounds Containing More Than One Chirai Cenere
In such cases the
contiguration about cach chiral centre is ascortamed
-OH HO H pee T
specification of cach atom alongwith its number is then prefixod before ths nze d
CoOH COOH
LTartaric ad
compounds as illustratcd below
DTartrc ad ()Let use consider onc of the forms of tartaric acid.
CHOHCoOH
Formulae
8.10.1 Configuration on The Basis of Projection
Wale assigning configuration to a stereoisomer on the basis of projection formula CHOHCOOH
the procedure is cssentially the same as in case of three dimensional formulae. However, if the Each chiral centre in this molecule has the same set of
four groups attachcd to it. The soquenoc of
group of iowest priority iS pointing towards us (i.e.. bonded horizontally) an additional step is pricrities of
thesegroups is OH. COOH, CHOH-COOH H Foloming
required In such cases the given formula is converted into another projection formula bymaking this sequence of priorities, the
two interchanges so that the group or atom of lowest priority is placed vertically downward configuraticns around each
of the chiral centres is S so that the
compound may be
oT upards Then the canfiguration is assigned following the usual procedure designated are(2S, 3S)-tartaric acid

cOOH
-C-OO
CH-CH
HO
CoOHA
 cONCEPTUAL ENGINEERING CHE.MISTRY
STEREOCHEMISTRY
cmpound
to the

assign
co7tguralion
8.11.1 Conformation of Ethane
nou
us
ud i C In cthant molecule. if it is supposed that the posttion of one of the casbon atoms s kept
and other
fivcd therespcct rotateid about it.
is large nunmber of arrangenents of the iy rogun of the
a

H-
carbun with to
th hv drogen of the other be obtancd Out uf the mfinite numther of
can

Possible conformations of cthane, two conformiations represent the estrenes. as shonn i

Fig 8) These arc
attsck.
C H,. H. Cl and CHCICH, d to it
2 and has the groups I Eclips.d contormation
Each ef carbou atoms of groups is
2 Staggered conformaton
Thc order of prioities

CI, CHCICH. CH. H Eclipsed conformation: In this confomaton. the tetrahedrally altached three ly drogen
at can be known as folloWs atoms to trout carbu are enacti in front ot those attached to the back carbou, c .
Configuration hydroyen atoms of both the carbon atoms are eronded together
CH

H-
(Aftertwo
CHCICH, crchanges)
CHCICT
Confiuation

follows 1
at "C can be obtained as
Condiguration

CHCICH CHCICH
H -(1 -CH Ecipscd Stnggerod
Aler twNo Fig. 8.9 Eclipsed and staggered conformations of Ethane
Interchanyes)
CH 2. Staggered conformation: In this conformation. the
Conliuralion R
atoms to two carbon atoms are as far
tetrahedrally attached bydrogen
apart as poss1ble. It is important to note the bas1c
is (28. R )
Hence the configuration of the above compound structur of the molecule and the various
bond lengths and bond angles remam the
same in both the conformations. These are called Sawlhorse nmethod of
the conformations. (Fig. 8.9) reprusentung
3.11 CONFORMATION OF ALKANES
Rotation around carbon-carbon single bond. Single covalent bond ( a bond) prescnt Newman's sty le of representing the conformations of' molccules is more
the two conformations of ethane popular Thus.
bctwecn two carbon atoms is formed by the overlap of their sp' hybrid orbitals along the inter may be represented by Newman's projections as shown in
Fig. 8.10.
nucicar axis. The clectron distribution of the molecular orbital. thus formed. is cylindrically
symmetrical around the asis of the bond Due to the axitl symery of the molecular orbital,
rotann around the C-C bond is almost free. As a result of this rotation, alkanes can have
diflernt spatial dtferent relative arrangement of their atoms
arrangements, i.c.
spac in

Sch diferci spatial urrangemeaty of dtoms or grous of atoms in a

ihat can he
molecule
inier-convericd hy otation uround
readhly sngle honl are called
cnjarner's They are rotational isomers and the phenomenon is called. conformational
he molecular
1s0meriSm
geometry corresponding to a contormer is known as conformation. Eclipscd Stagrcred
Fig. 8.10. Newmen's projection for the
conformations of Ethane.
 ONCEPTUAL ENGINEERING CHEMISTRY
STEREOCHEMISTRY 353
circles
represented
are
bond
a

the tiwo
carbons
foring

is
scen.
The
hydrogen
atomsa

H
ttached to the eclipsed and staggered, is 13.8 kJ mol
which is nearly the same as in case of ethanc. The
362
In Newman
projection.
only
the front
carbon

centre
of the
circle. he CC
The --

Hbonds of the most stable conformation is the staggcred conformation although it can freely change into the
so
that from the
the other,
H
bonds
circle. cclipsed conformation and vice versa.
C of the
-
behind
one depicted by circumference

front
carbon
are

drawn
from the
converted
into the other when rotated
through an H H
back
carbon

Onc
are

conformation
of cthane gcts
CH3
angle of 60 H CH3
c o n f o r m a t i o n s
of e t h a n e .
stabilities of
Relative that
out here
It must be pointed not
bond is
single H
rotation
a r o u n d the
potential H
H H H
If it vwereso, the H
completelyfree. conformations
should
diffcrent
of Fig. 8.12 Newman's projections for the conformations or propane.
cncrgy actual practice,
But in
have been the
same.
molecule changes Conformations of n-Butane
the potential energy
of the
C-C
8.11.3
the rotation around 12.6 kcal
somewhat with
of H
Thus the potential
energy per mole H H H
single bond. for staggered
is minimum
ethane molecule
conformation and maximum

difference between the

for eclipsed H-c-C-c3-ci-H
conformation. The
H H H H
mol. In other words, H
two being 12.6 kJ
is the most If consider the rotation around the single bond between two carbon
we
Staggered conformation atoms (C, and
stable conformation of
ethane while C3) of n-butane, we see that molecule is similar to ethane except that one hydrogen on each
is the least stable carbon has been replaced by a methyl
echpsed conformation Staggered group
(Fig. 8.11). Fig. 8.11 Relative stabilities of H H
diffcrence conformations of Ethane
The small
energy
between different conformations is duc to (i.e., CH-2C -c3 - CH)
bonds attached to the central
the repulsive interactions between the clectron clouds of the C-H
C-C bond. In the staggered conformation of ethane, the clectron clouds of these carbon hydrogen H H
bonds are as far apart as possible. But in the eclipsed conformation, the three C-H bonds of The various possible conformations of n-butane are:
one carbon are closest to the three C-H bonds of the other carbon. The repulsive

between tHe clectron clouds in this position increase the energy of the molecule and
interations (i) Anti conformation (): In this conformation,
methyl groups and hydrogen linked to
thus two carbon atoms (C2 and
C3) are ata maximum distance apart. It is
decrease its stability. angle of rotation around the C2 -

C3 assumed that the

bond is zero for this conformation.
5ut is not to prevent rotation. Even at
the energy difference ordinary
large enough
temperature, the molecules possess sufficicnt thermal or kinetic energy to overcome the energy
(ii) Eclipsed conformation:
Starting from the anti conformation, if we rotate the
single bond through 60°, we get the C2 C3 -

barrier through effective collisions and thus conformations

kcep on changing from one form methyl group attached to one carbonpartially eclipsed form II. In this conformation, the
atom is at the back of
the other. As such it is not the methyl hydrogen atom (rather than
to possible separate the different conformations of ethane. group) attached to the other carbon atoms.
(iii) Gauche or skew
8.11.2 Conformations of
Propane configuration: On
get the staggered conformation. lll rotating C^ C single bond by another 60°, we
-

is also
In case
of propane (CH3 CH -CH) -

rotation can take place about either or ne

conformation, the various bonds are farthest known as gauche or skew form. In this
carbon-carbon bonds. The of 60° with apart but the methyl groups make an ang!e
energy difference betwecn the two extreme respect to each other.
conformations
 ING CH
cONCEPTUAL ENGINEERING CHEMISTRY
60s
by another 60°
bond by
bond
another gives rise to STEREOCHEMISTRY 355
C-C
C;
ups and hydrogen
Roratin8
the
Cvontomatton,
the meth
conformation;

in thus
ect1pse
cach other. (IV). Thus. partially ectipsed conformations are more stable than fully cclpsed
eripsed {i\)
t ) Fat
ovufornathon
atoms
comypletely

which the
the nm
methyl group conformation.
drd carbon
torm (V) in

t m
io gauche
atwas
artachad

v . a t m
otou g n s
ris to the
nd by
o0,
we get
another

the rotation
eclipsed .

conformation (ii) In gauche conformation (1ll and V) there arc weak repulsive interactions betwcen two
methyl groups as they are 60° apart. In other words, there is a slight Vander Walls
Futhr
rotating -C thus.
thus
completing
we
a
further
o0 and
by o0 and strain but no torsional strain. Thus, i is more stable than partíally eclipsed
aa od anart rotaton
oftC- C;
C -C;
Siil
arthor Confor7nation.
13
(1 n Fgure S.
Ha CH3
shonn
cmfommatrons
ar
CH3
1he
1arious CH
CH HC
HC
H HH H-
Fully Eclipscd
H H

Eclipsed Eclipsed
CHs

CH CH3
18.4 KJ/mol
CH
CH CH
H- 14.6 KJ/mol 14.6 KJ/moB

H
3.8 KJ/mol 3.8 KJ/mo
-- - - - - - - - - .
H
H CH3 CH3 CH
H H,C
VI
Y CH3
Fig. 8.13. Newman's projection for the conformations of n-butane
CH,HH H H°
CH3
H
H CH
of n-Butane Anti Gauche
Relative stabilities of conformations Gauce Anti
The stability of conformations of n-butane is in the order 60° 120° 180 240° 300 360°
Gauche anti Rotation
Fully eclipsed partially eclipsed
Fig.8.14. Energy Changes during rotation around
aV) (II and VI) (III AND V) () the carbon-carbon bond in n-Butane.
(iv) In anti
conformation (I), the repulsive Interaction between
the two methyl
the bonding electrons is minimum because the two groups and
) In fully eclipsed conformation IV, there is maximum repulsion between bondng apart. Thus, this conformation is free methyl groups are maximum distance
electrons and bulky methyl group. Repulsion between bonding
torsional strain in the conformation while the crowding together of the bulky
electrons produces is the most stable
conformation.
of torsional a s well as steric strain. Hence it
metny
group causes steric or Vander Walls strain in the molecule. Due to torsional straln an (v) As anti conformation and Gauche
conformations have staggercd
steric strain, this conformation has maximum
energy and minimum stability
have maximum
energy and maximum stability (anti conformation is arrangements, they
i)
than Gauchc
conformation). These conformations are referred to slightly more stable

In the partially eclipscd conformation (l VI) the repulsive interaction

and betweenthe isomers. as conformational

Dulky methyl group and bonding electrons is less than in fully cclipsed conformatio
 CONO

I IV is
HEMMSTRY STEREOCHEMISTRY
contormations
and
about 18.4
betwcen
d ki
(Il or V)s
betiwcen

contents mol-' and

kJ
J56 in energy
is about
14.6. This make the s-orbital as the boundary orbital in a neutral atom
II (or VI)
difference

The
(i) betveen I and ie
mol,
8 kJ mol
between
two
conformations

temperats
18.4 k/mo Table 8.1.Outer electronic configuration oftransition metals.
only 3,
Therefore, the
difterence

room
encrgy molecules at
masimum

the colliding and hence nnot be isola First Transition (3d) series (Sc-Zn)
(vii) As providcd by inter-convertible

is easily are
bond in n-butane
is aln
which
conformations
of n-butane
carbon single free. At any 21 22 23 24 25M 26 27 28 . 29 29
various around of all the possible
of
In other
words
rotation

consists of an
cquilibrium
mixture

anti conformation(s)
andi formations Ar13d'4s2 3d 4s 3d 4s 3d 4s' 3d 45 3 4s 3d' 4s3d 45 3d 4s' 3d 4s
time,
n-Butanc

highest percentage
of the
ortion Second Transition (4d) series (Y-Cd)
contains the (iv).
which conformation

of the fully
cclipsed 29Y 402 41th 42M 43T 44P 45T 48P 47
COMPOUNDS [Ar14d 5s2 |4 5s 4d s' 4d 5s' |4d 5s' 4d' 5s' 4d ss'4d 5 4 ss' 4d 5s3
METAL
8.12
ISOMERISM IN TRANSITIONAL Third Transition (5d) series (La- Hg)
57La nHf T3Ta 74W 75Re 760S 7 7aPt Au spHg
Transition Elements
which eithcr in
tneir elemental state or in their en.

mmonly
|Xe]5d'6s 5d 6 5d 6s5d 6s 5d 6s 5d 6s 5d' 6s5d es'Sd 6s Sd 6s
are those
The transition clements
d- and f-shell. By this definition we here Fourth Transition (6d) series (Ac- Mt)
have partly filled
occurring
oxidation states
elements usually
are called transition element and f
clements. d-block
a9AC 104Rf 10sHa 106Unh 107Ns 102HS 1 *11

block and f- block transition elements. Rnj6d' 7s6d 7s 6d' 7s 6d' 7s6d 7s6d 7s 6d 7s
are called inner
block elements show a sloW and gradual cha Show irregularities in configurations.
The transition
elements are the
elements which Change
s-block clements on one side and p-block clement on
between highly reactive
characteristic
their position in the periodic table where
table. It is also from hey 8.12.1 Complex Formation by Transition Elements
the other side of the periodic electronegative p- block elements and
s- and the
most thus
lie between the most clectropositive Transition metals form a large number of
complex compounds. Here the metal ions
from them and are called transition elements. They are al bind number of anions or neutral molecules
rcprcsent a transition (change)
a
are added in the d-orbital of the (called ligands) giving compounds showing
because the successive elcctrons characteristic propertics. Some cxample of such
called d-block elements complex compounds are:
shel. Their last two shells are incomplete. They lie in the groups 3 to
(n-1) or penultimate
12 in the periodic table.
FeCN). IFe(CN),IH ICu(NH,)1*. IPtCI
Their tendencyto form
the celements in which last electron enters complexes is due to the following reasons
Thus, the d-block elements are defined as ) The prescnce of vacent
nexi to the outermost shell.
(n-1) d orbitals which can accept one or clectron
in d-sub shell of their penultimate shell (n-l) i.e.,
more
from ligands. pairs
(i) High charge density due to small size and
Electronic Configuration of Transition Elements high charge of the transit:on metal 1on.
(i) Availability of several oxidation
The d-block clements are classified as transition serics of clement with
states
4d, Sd and 6d orbital. They are made up of three complete rows of 10 clements cach and an
incomplete34 A complex molecule consists of a
highly charged positive metal ion
incomplete fourth row in the long form of periodic table.
vacant d- orbital
capable of receiving lone pairs of electrons form ligands(Lewis acid) with
attached to the
central metal ion or atom to fornm a
metal atom or ion.
complex ion is called co-ordinate number of
the central
Caution. Although the As- orbital penetrates closer to the nucleus than 3d orbitalsand
therefore, has lower cncrgy, the convention for writing the electron notations of transiuon The stability of the complexes increases with
clements is to write electrons in (n-1Jd and n s-orbitals. There are two reasons for inerease in atomie number of the element
this Morcover, the complexes of atoms with higher oxidation
states and thus smaller size arc
(a) lonization of transition metals is duc to loss of ns-electrons (of course with more stable. relativcly
excu
(6) The probability plot of ns clectrons shows
that these electrons have a greater pr
Complexes have linear, square planar, tetrahcdral. octahedral, square py ramidal or
of being far from the
nucleus, while
trigonal bpyramidal structures depending upon the type of
the (n-1) d clectron are relatively burncus hydridization involved during their
inside the atom. formation.
 CONCEPTUAL ENGINEERING CHEMisT

Complexes dination Type of Structure

369
358 Lewis bases Number
hybridization STEREOCHEMISTRY
Lewis a c i d s
Ligands (donors)
() ICo(NH),(H,0)CIjCI, and [Co(NH,),Cl,)CI .H,O
(acceptors)

(Centralmetal ions)
Sp i) [Co(NH) (H,0)CIJBr, and [Co(NH),Br,]CI. H,0
AgNH)
2N dsp2
Linkage Isomerism. Isomrism of this type occurs when more than a single
atom im
CuNH) 5.
Ag 4 NH3 a mono-dentate igand may function as a donor. For example, in the case of NO
Zn(CN)2
sps
Cu isomers.
4CN ion cither a may act as donor giving two
nitrogen or an oxygen atom different
Zn2
6 dsps Thus two different isomers with molecular formula [Co(NO,)NH,);}=* have been
6H,O
Cr(HO
linked cobalt atom and the other
C prepared. One isomer has N-atom of group NO, to

has 0-atom linked to cobalt

Transition
Metal Complexes
Isomerism in
8.12.2
two main types
of isomers
NH3 NH3
There are
(A) Structural Isomerism HN ONO HN NO2
isomerism
or stereo
(B) Space
NH3 NH3
(A) Structural Isomerism
HN HN
mainly ofthe following
types NH3 NH;
It is
different 1ons in solution although th
Ionisation isomers yield Nitroperitamminecobalt (II1) ion (Ycllow)
lonisation isomerism.
of isomerism is due to
the exchange of groups between Nitritopentamminecobalt (IlI) ion (Red)
This type
have same composition.
outside it, 1.c. in 1onisation sphere. For examnla Other Examples are:
the ions
the complex ion and with BaCl, confirmino () [Cr(H,o)),SCNJ** and [Cr(H,0),NCS]2*
red-violet and in solution gives a precipitate
Co(NH)Br]S0, is
the presence of SO
ion.
ci)[ONH,)2(Py),Co(NO,)INO3 and
[(NH),(Py),Co(ONO),INO; ete

is red, and does not give test for sulphate ion in 4. Co-ordination Isomerism. This type of isomerism is possible when both positive and
On the other hand. [Co(NH3),SO,]Br
of AgBr will AgNO3. of a salt are complex ions. The two isomers differ in the distribution of
the solution, but instead gives a precipitate negative ions
ligands in the cation (positive ion) and the anion.
isomerism are:
Other examples of ionization
Two important cxamples are:
PL(NHy)a(OH),IS0, and |Pt(NH3),SO,l(OH),
() [Co(NH)%l ICr(CN)%l and ICr(NH,)] ICo(CN)sl
ci) [P(NH,}ACI%]Br, and |Pt(NH3),Br,|Clh
ci) [Cr{NHy)%) [Co(C,0sl and ICo(NH3),1 [Cr(C,0,)3]
Ci) (Co(NH,)SNO,IS0, and [Co(NH3),SO,INO,
(ii) [Pt(NH3)al [PtCI,l and |PtCL,(NH,),I [PtCI,l
Hydrate isomerism. Since water is one of the most effective co-ordinating agents, This type of isomerism may be caused by
thercfore, the number of water molecules which may enter into the co-ordination sphere
interchange of ligand between the two complex ions
For example, there are three
5. Co-ordination position isomerism. This type of isomerism is due to the
may vary resultüng in the formation of hydrate isomers. in the distribution of ligands in two coord1nation centres.
difference
different hexa-hydrates of chromic chloride with an empirical formula of CrCl3.6 H,0. Generally the bridged
One of these hydrated is violet and the other two are grecen in colour. complexes invoBving dilferent ligands show this isomerism e.g.

differ in the number of molecules of water in the co-ordination sphere. The formulac
All the thre 12+ 2+
which have been assigned to these hydrate isomers are: OH OH
ICrH,0),1Cl Cr(H0),CIjCi. H,0 Cr(H,0),Cl,JCI. 2 H,0 (HN),Co Co(NH)C1| Cl(HN);Co Co(NH hCI
Violct OH OH
Bluish green Dark green
(three ionic chlorines) (two ionic chlorines) (one ionic chlorine) Unsymmetrioal Symmetrical
Similarly other compounds in which hydrate isomerism is observed are : 6. Ligand Isomerism. This isomerism arises in those eomplexes in which the two ligands
are isomers themselves. e g.
 361
cONCEPTUAL ENGINEERING EMISTRY STEREOCHEMISTRY

H2
-CH2 ¢H2 NH3
NH2 NH3 H3N
H C - C H - C H 3

and
NH2 H3N
trans-
1,3-diamino propanee cis-
NH2 and MAB, do not show this isomerism
NH2 (ii) Complexes of the type [M(AA)]. MA4, MAB
1,2-diamino propane
isomerisnm for any of these complexcs are identical
1 his type of since all possible spatial arrangements
c.g.
isomers.

we get ligand
In a complex of thc type MA2BC, also
there are is-and trams-isomers,
the complexes, (ii)
these form it exist as:
When
isomerism
because occurs
en
[Pt(NH3),CINO,] can
not true
rare. isomerism.
This is

formula,
but
ditferent
molecular weiohto
O,. O2N NH3
Polymerisation
same
empirical empirical formula.
having the
same
have the
compounds [Pt(NH;)4][Pt©CG]

[P(NH),Ci]
and
H3N NH3 H,N
Isomerism
cis- trans
o r Space ligands. It is of two types:
(B)
Stereoisomerism

different
relative positions of the (iv) For a complex of the type MABCD, three isomers are possible, e. g. [Pt(py)(NH3)BrC]
to the
This is due can exist as:
(1) Geometrical isomeris
(2) Optical isomerism
the geometrical isomerism HaN y HaN- HaN Br
investigated is

Out of these two, the most thoroughly Pt

isomers differ in the spatial distribution
ution
isomerism:Geometrical Br Br- >CI CI
Geometrical compounds. Those complev
lexes
(1) atom or atoms
in polynuclear
(v) The geometrical isomerism can also occur in square planar complexes if the chelate
about the central to cach other
to cach other or opposite group is not symmetrical, e.g. [M (A-B)2]. for example, complexes between glycine
ofatoms or groups ligands occupy adjacent
positions
in which thetwo same
show this
isomerism. (NH2CH2COOH) and platinum i.e., [Pt (gly)21.
a r e able to
trans respectively)
cis or
by co-ordination compounds having 2 or 3
H2C-H2N NH2-CH2 HC-HN- -CH
isomerism cannot be exhibited
This
to have more than a Single arrangement of
umber as it is not positive
co-ordination
cases.
G e o m e t r i c a l isomerism with respect
Ceniral-ion in these
ligands in space around the or MA B OC- CO OC-
tetrahedral complexes of type MA, NH2-CO
not been found among
to the metal has also from each other. cis-
because all the four ligands are equidistant trans
which do not show this isomerism
planar and octahedral complexes. (vi) Geometrical isomerism is also shown by bridged binuclear
planar complexes of the
This type of isomerism is shown by square
type, M2A4X4, C.8., [PtCl,
(a) Cis-trans isomerism in square planar
complexes is of various types: PEtzl2
Cl
(i) Any complex of the type MA,B, can exist
in cis-trans form.
CI CI PEt3 CI
A B,

PEt -ci EtP CI Et3P

3 B A B CiS
trans-
cis- trans- (b) In octahedral complexes,
several kinds of cis-trans isomers are known the most
It is because the ones being cis-trans isomers in important
ligands may be cquidistant from the central atom, they are not equidistan MA,B, and the cis and trans isomers in MA,B3.
from each other. Conscquently it is possible to distinguish between ligands that lie next (i) Example of the MA,B2 type octahedral complex is furnished by dichloro-
to cach other on the edge of the square and those which lie opposite to each other on tetramminecobalt (1I) complex ion,
the square diagonally. given below: [Co(NH3)Cl1. It shows cis-trans isomerism as
For example, the square planar complex of the type MA,B, i.c, cis-platinum or hloro
diammine platinum (11), [Pt(NH3),Clh] can cxist as under:
 cONGEPTUAL
ENGINEERING CHEMISTRY

363
STEREOCHEMISTRY
C
behaviour
ISomers of a compound called enatiomers or enantiomorphs. The physiological
are

C
HN NH ofthe enantiomers is quite different e.g.. 1-nicotine present
in tobacco is quite toxic than d

nicotine prepared in the laboratory

H HN NH3
8.12.3 Optical Activity in Octahedral Complexes
Cl
2 or 3 sym1metrical bidentate
HN
trans Grecen Optical isomerism is common in octahedral complexes involving
NH; two co-ordinate bonds) of the type:
groups (i.c. a group attached to the central atom by
complex is furm
shod by [Co(NH)
cis Violet It and where AA =
bibentate ligand
MA,B; type
octahedral
[M(AA),Xl [M(AA)I
of the isomers.
Example gevmetrical

shows the
tollowing
two
NH3 This is illustrated as under:
NH NH3 (a) Example of M(AA),X2 type:
NHs The complex ion is cis-dichloro bis (ethylene diamine) cobalt (1lI) ion. [Co(en),Cl,l'.
due to the
The above two are optical forms. There is also an inactive transform
HN presence of a plane of symmetry
and is shown below:
NH C
trans-
C
CIS CI CI Cl
also show eis
ans isomerism, where AA can
and trans
npe of compleves B can be any anionic li.
() Even M(AA),B,
bidentate like
ethvlenediamine (en)
and
ligand CI

be anv symmetrical
C. CN". NO:
etc.
B n en
such as

en
CI

Mirror Optically inactive form

B Another
trans
example is
[Pt(en),Clo]l
cis (b) Example of M(AA)3 type:
Another example of this type is [Pt(en),Ch
isomerism.
Examples of the three bidentaite ligands inoctahedral complexes are [Cr(en),15*, tris
Note: ) MA,B] does not show geometrical (ethylene diamine)-chromium (U1) ion and [Cr(C,0), trioxalato-chromate (l) ion.
isomerism.
(ü) [M(AA);F" does not show geometrical
exhibit geometrical
(iv) Complexes having six different ligands [M(ABCDEF)] shajl
isomerism. Theoretically fifteen different isomers should be possible. In practice, three
isomers of the complex [Pt(CHNJ(NH)ONO,NCI)(Br)()] have actually been isolated.
2. Optical isomerism: Optical isomerism arises when a compound can be en
represented by two asymmetrical structures (known as optical isomers). The two isomers are
structurally the mirror image of each other (just as in the organic chemistry). Further it has ben
found that these mirror image compounds are non- superimposable on each other en en
not possess the plane of
and ney
symmetry. The optical isomers are called dextro and laevo (a anu
depending upon the direction in which plane of the polarised is rotated. Then d
light and Mirror
 cONCEPTUAL
ENGINEERING CHEMSTRY
STEREOCHEMISTRY 365

OX

Ox
0--0=o
The two enantiomers of bis (benzoyl-acetonato) beryllium (11) arc shown below:

Mirror

M (AA) B,X,
type:
bidentato Me Me M Me
Examples of containing one symmetrical
(c)
of the formula
[M(AA)B,X,| C=O 0=C C=0 0=c
Compounds
activity, eg
also show optical
CoCi,0NH3)(en)]. [PiCl,Br,(en)}. Be CH HC Be CH
0
CI Ph
C
Ph Ph
CI Cl Mirror
Cn
en It may be noted that 4 different groups around the central atom are not required for
Optical activity. All that is required is that the molecule should be dissymmetric so that it can
NH NH exist in two forms which are mirror images of cach other, as shown above.

NH NH It may also be noted that chelate groups are not required, as a principle for
optical
activity However, most of the known examples involve chelate groups. This is probably
Mirror due to greater stability off such complexes which makes thcir resolution
possible.
Square planar complexes are seldom optically active. One such compound which
8.12.4 Optical Activity in Tetrahedral Complexes has been resolved into two forms is shown bclow:
has been observed for chelated
tetrahedral and square planar
optical activity
The
complexes but only rarely.
In tetrahedral complexes only the type which occurs in bfc-chelates with unsymmetrical

ligand has been detected. These have been found in Be(II), B(1I), Zn(II)
an Cu(11) complexes H2 2
Ph *H
They are of the general type as represented below

Me Me
NH NH
Ph Me
Mirror As can be seen, it has axis of symmetry.
Thus
no plane or
bis(salicylaldehyde)
has been accomplished.
boron (H) cation has been found to be recemic and resoluion
 cONCEPTUAL ENGINEERING CU
AISTRY STEREOCHEMISTRY 367
Solved Typical Problems

-Br(2)
exhibit optical isome
isomerism:
following
compound
will
H-C Vicwer S (Anti-clockwisc)
Which of the (b) CHCH(OH)CI
Problem
1.
c)CH,CHCH(Br)CH,(CH)
(a) CH,CH(OH)CH,
(d) CH,(C)CH,OH
Br(2)
(e)CH,CH(OH)CH(OH)CH

and (e).
because they contain chiral (or nmctric) carbon
asvmmete:
H- Viewer .S(Anti-clockwise)
Solution. Compounds (b). (c) H,C Br(1)
atom o r atoms.

Br QH OH COOH(
OH Vicwer
HC-CCl
CH-C-CH(CH;)% H,c-¢-¢ (1DH
H-
CH,(3)
R(Clockwise)

H H
H
(e) COOH (2)
(c)
(b)
carbon atoms and give
the number of optical isomer. H- Viewer . S(Anti-clockwise)
Example 2. Mark the asymmetric HOOC(CHOH).co0u H,C OH0)
in the
(a) CH,(CHOH),COOH, (6)
following compounds:
OH
Problem 4. What is the necessary and sufficient condition for a molecule to be optically
Solution. (a) Compound : H,C- -c-coOH active?

Solution. The necessary and sufficient Condition for a molecule to be optically active is that its
OH OH
molecule should be chiral, i.e., the molecule and its mirror image should be non super-imposable.
Contains two asymmetric carbon atones.
isomers 2 =
4. Problem 5. Does the presence of one chiral carbon atom make the molecule optically
Theresore, number of optical (d-and )
-

active ? Explain.
H Yes. The presence of chiral C-atorn in
Solution. one a molecule always makes it chiral and
(b)Compound:HOOC-C -COOH hence shows optically activity.
Problem 6. Does the presence of two chiral carbon atoms always make the molecule
Contains two asymmetric carbon atoms, but it can be divided into two equal halves, so
optically active ? Explain.
number of optical isomers = 22 - 1 = 3.
Solution. Not necessarily. The presence of two similar chiral carbon atoms
may or may not
Problem 3. Assign R and S configuration for each of the following compounds: make the molecule optically active. If the molecule as a whole is chiral, it is
optically active and
if the molecule as a whole is achiral, it is
Br Br COOH COOH optically inactive, For example, (+)-
tartaric acid. and (-)-tartaric acid are optically active because their molecules are chiral, i.e.
i) H- (ii) HC iv) H- (v) H-C the molecules and their respective mirror mage are
non-superimposable. On the other hand,
H,C Br HCH HC OH mesa-tartaric acid is optically inactive because its molecule is achiral. i.c. tho molecule and its
mirror image are superimposable due to the presence of a
plane of symmetry in it.
Br2)- However, the prosence oftwo dissimilar chiral carbon atoms always makes the molecule
optically active.
Solution. )
Viewer R (Clockwise) Problem 7. How many pairs of enantiomers are possible for the compound, 2,3-
dichloropentane? Explain.
 cONCEPTUAL ENGINEERING CHEMISTRY
STEREOCHEMISTRY
38
activc
f 2,
forms of 2, 3-dichloroper
3-dich

optically
four
1c
168 enantiomers, Mirror
Tivo pairs
of Plane of
Sotution. COOH COOH CoOH
potsible Thcse are
Mirror symmetry
H- -OH HO H OH
Mirof CH CH ---

CH3 H- -OH
CH H- - C-C-H HO- -OH
CI-C-H
H--C H-C-CI C0OH coOH COOH
C-C-H
C--H (Meso form which is optically inIcthve)
H--C
CHCH
CHCH H,CH Pair of enantiomers, which are opticaly active)
CH,CH Enatiomers- Thus, there arc three forms of tartaric shown above
Enatiomcrs- Dextro or + form of tartarnc acid
a molecule opticat ()
of chiral
carbon atoms, always make
otically acid
Problem 8. Does
the absence (n) Laevo or form of tartaric
inactive? Explain. it t is non- superimposable on (n) Meso tartaric acid. which is optically inactive duc to internai compensatio
1s optically
active its
A molecule which contauns( nd (-) form n
Solution. Not neccssarily carbon atoms.
For examplc, 6, 6'-dinitrodinh There can bc a recemmc mixturc ( tartanc ac:d).
contain chiral
It may or may not
do not contain chiral carh cqual amounts. It is optically activo duc to cxternal compensaton
mirror imape
active evcn though. they,
3-dicnc are optically and their respccti
acid and Penta-2, chiral, i c., the molcculcs
pec Problem 12. What will happen if one of the OH groops of tartaric acid is replaced by
thesc molccules arc
that
being
atoms.The reason non-super1mposable
mirror images arc
NH,group?
are present in the molecule, Solution. If onc of the OtH groups of tartanc add is replaccd by NH, group. possibie contigaration
chiral carbon atoms
Problem 9. Haw Many
HOCH-CHOH-CHOH-CHOH-CH,0H
will be

stereoisomer are possible for this compound ?

and how nany optically active Mirror Mirror
Solution. The compound, COOH COOH COOH COOH
H NH, HN H Ni H
HOCH, CHOH-CHOH-CHOH-CH,OH
astcrisks The middle carbon atom HO H H O H OH HO H
coniauns only samilar chiral carbon atoms as marked by
two

15 symmctrically any substitute and lhence 1s not

chral Therefore, Iikc tartaric and, it also exists COOH COOH COO COOH
in threc stcrco-isomeric forms. ic (). (-) and meso () () u)
Probiem 10. Which of the following compounds would show optical isomerism (Enantiomcrnc pair) (EzartiomcTic ar
(6) HN.CH,.COOH (i) (CH3) CH.CHO Thus, number of optically active forms will 3crcase Beside the above four forms,
tii) H,N.CH.CH} cOOH
(iv) CH-CH (OH) there are diasteriods. Structure (uty ts drastersod of structure () Simarty stracture fu) is
diasteriods of structure (u) and so on
COO
Problem 13. Give examples of optically active conpounds with out chirality.
Solution. (v) H,C-C-O1, will show optical isomerism, as it possesses chiral carbon atam
Solution. There are many compounds whuch do not contain chrai carbon atonms but ther
CH molccules are chural or
markcd wIth asterisk *
disymmetric
and hence show enantuomersm optical or act
For example, allencs and o-5ubsututed d1pheny ls do not contain chral carben atoma bat
Problem 11. Discuss stereochemistry of tartaric acid. thcir molecules are non-superimposable on ther tespcctive murror images and bence thow
Solution. Different configurations of tartanc acid are as under CrtantiomtISm or optical actiVEty
 cONCEPTUAL- ENGINEERING CHEMISTRY 371
STEREOCHEMISTRY

CHy according to the 1UPAC system. Which

Mirror Problem 15. Name the isomeric forms of
CH one(s), if any, is (are) optically active?
CC=C Solution. CH,CH,CH,CH,CH,CH, CH,CHCH,CH,CH, CH,CH,CHCH,CH,
hexane CH CH
CH HC 3-methylpentane
2 methylpentane
Enantiomcrs of CH
penta-2,
3-dienc Anallene H,C-CH-CH-CH H,C-CCH-CH
Mirror
NO2 HOOC
CH CH CH
2,2-dimethylbutane
CoOH O2N 2,3-dimethylbutane
Nonc of these isomers isoptically active.
difference between a meso-isomer and a racemic mixture.
coOH Problem 16. Explain the
HOOC What characteristic(s) do the have in compound?
NO2 dinitrodiphenic acid Solution. Ameso isomer is a single compound, a
racemic mixture contains an cquimolar mixture
Enantiomers of 6, 6'
of two compounds. The meso isomer is inherently inactive because of internal compensation;
not ? Explain. (UPTU, 2010) because the cffect of one of the
are optically nctive or the racemic mixturc does not rotate the planc of polarizcd light
Problem 14. The following compounds isomers negates the effect of the other. The racemic mixture can be separated into two optically
(b) 1, 7-Dicarboxylspirocycloheptane
(a) 1, 3-Diphenyl propadiene becausc its structure shown below active compounds by physical means. The meso isomer and the racemic mixture have in common
is optically active,
Solution. (a) 1, 3-Diphenyl propadiene their inability to rotate the planc of polarized light. Both have two centres of (opposite) chirality
molccule.
confirms it to be a dissymmctric
Mirror Problem 27. Tartaric acid is dilydroxydicarboxylie acid, HOcoCHOHCHOHCO,H.
Identify any chiral centres, draw all optical isomers, and explain the total number of
Ph Ph such isomers of tartaric acid in terms of the 2 rule.
Solution. The two middle carbon atoms in each structure are chiral centers. They are starred,
Ph to indicate their chirality.

CHH CHH CHH

The above two structurcs represent a pair of enantomers of I, 3-Diphenyl propediene,
which are non-suporimposable mirror images. H-C-OH H-C-OH HO-C-H
(b) 1,7-Dicarboxylspirocycloheptane is also optically active.Spiranes arc compounds havinga H-C*-OH HO-C-H H-C-OH
carbon atom common to rings. The two rings are perpendicular to cach other. Spiranes exhibit
CHH CHH CHH
optical isomcrism because of restricted rotation as shown below. meso
Mirror There are 3 isomers instead of 2 4, one a meso isomer.
COOH HOOC Problem 18. (a) Draw all the stereoisomers of 3-chloro-2-pentanol,
HOOC H CHCH(OH)CHCICH,CH
COOH
1
(b) Give the stereochemical relationships of the stereoisomers.
The above two configurations represent a pair of enantiomers Solution. (a) There are four stereoisomers. A and B are enantiomers, as are C and D.
of 1, 7-Dicarboxyl
spiroeycioheptane, which are
non-superimposable mirror images. (b) A and B are diastereomers of C and D.
 cONCEPTUAL ENGINEERING CHEMMSTRY 373
STEREOCHEMISTRY

CH CH3
Problem 23. Draw and specify as R or S enantiomer (if any) of:
CH H 0OH
372 CH HO H (a) 3-bromohexane (b) 1-cleuteno-1-chlorobutane
H -OH
H -C
HO C H H H
H -CI
CHs CHs Solution. (a) n-CgH-CHs HC2 -CgH7
CHs (C) (D)
Br Br
(B not:
(A) are optically
active or S
compounds
The following (iv) Allenes
Problem 19. 2-chlorobutane Br> C, C. C >C, C, H>H
(i) n-butano (ii)
) n-propanol chiral carbon.
inactive because it has no H H
is optically
Solution. (i) n-propanol D--nC3H7
CH-CH- CH-OH (n-propanol) (b) n-CgH -D
has chiral carbon. C CI
inactive because it
no
n-butanol is optically
i) OH (n-butanol)
CH-CH- CH, CH,
-
-

has a chiral carbon.

CI>C>D>H
2-chlorobutane is optically
active, because it Problem 24. Draw steriochemical formular of CH,CHBrCHOHCH and give R/S
(ii)
CH-CH CH -OH designation.
Solution.
CH2 CH CHs CH3 CH
(2- chlorobutane) H -OH HO H H -OH HO -H
do not contain any chiral carbon.
(iv) Allenes are optically inactive because they H Br B r -H Br H H Br

(Allenes) CH CH CH3 CH
2s, 3R 2R, 3S 2s, 3S 2R, 3R
active? Explain
Problem 20. Are all optical isomers necessarily optically Enantiomers Enantiomers
isomers are optically inactive, despite being
in the class of optical isomers.
Solution. Meso
Problem 25. Draw the enantiomers of (a) chloroiodomethane sulphonic acid and label
Problem 21. How many optical isomers can exist lot 2,3-butanediol? Would all of these each as R or S.
be optically active?
Solution.
Solution. There are three optical isomers, one of which is inactive (the Mese form) because of C CI
the two carbon atoms having the same groups arranged in opposite configuration.
Problem 22. Give the R/S designation for each of the stereoisomers of 1,3-clibromo-
-soH HOS
H
2-rnethylbutane. R
Solution. There are two chiral C's (C and C), and the four stereoisomers are shown below
with their designation.
Cl>S>H
CH,Br CHBr CHBr CHBr
Revision Questions
-CH HC H H- -CH, Hc H
H Br
BrH Br-H H- Br What is optical isomerism? Classify the different types of isomerism giving an example of cach.
CH3 CH CH CH 2. Differentiate between structural isomerism and stereoisomerism giving two examples of each.
2s,31 2R,3S 2S,3 2R 3R
 cONCEPTUAL ENGINEERING CHEM 375
1STRY STEREOCHEMSTRY
formnla C,H,0 and give UPAC Why their electronic configuration are nof ss
moecular
by Write the electronic configattion of Cu and Cr
sirnctural
zsomers
h ing pCr normal nules
the possibic
Re
taking
Aceto-aOctic ester as an example
Discass strectaral isomerism shown by transition clements by giving at least one examplc of
tautosens "Expiain
tatomernsm for optical activity
W a t js
"Chiralits
Is the essental
condition
Justify the cach type of structutal isomerism
exanple of each
Whatis ptical somcTism 17 Explain stereo-isomerism showzt by transition eiements by gviny at least one

its specification" Give in detal type of sterceo-1somerism

oonfiguratbon and the
understand by Absolute with coorfination ammber 2 i and
6. Give their
wiat do vo
illhustrate your
a n s w e r mith examples I8 (a) Give an esamplc of transiton mctal compier
ruics and
soqucncr formulac are possible stracture and name
activc forms
corresponding to the following
Hom many optically
6 (a
a OHC-HOH -CHOH-CHOH
) CH,-CHOH -CHOH-CH, (b) Gie one evample of cach
(m) Hydrate smerism
(iv) CH,-CHOH-CHOH ) lonisation isomerism
m) CH,-CHO -CHBr-CH, iUPAC
give structures and
names
characteristics. Also
Wrine down their main exnpkrs In Cch case
b)What aseenantiomern? 19 What is Geometrical isomerism of trans1tion matai conoleves. Grve no

Write short notcs on

b) Sawborse formulac
for
a) Fisher fornulac i)Octahedral complexes (i Tatrahedrai complexes

c) Ncwman formaulae d) Causc of Optical isomcrism 20. (a) What do you know about optical isomerisn in transatios cuzmpierues" Crve an exampke of Vi AAiX.

&ta) Anacid having noiccular forrnalac C,H,O, opticailly

is active What is its structure and nameof type complex showing optical actvtty

thc compound" Wrntc structurc of tts cnantiomers (b) llustratc with an example of optical actvtty shown by 2n octabedrai compiex
(b) Distingaish betucen acso and raccmic
forms of tartaric acid 21. (a) Draw and specify as R or S enant:omer (uf any) of
9 (a) Give various cascs of specafscation of oonfiguration whcn optical isomers are represented by
() 3-bromohexane (11) 1-cleutno-1-chlorobuiane
cross formuda (b) Give the R/S designation for cach of the stereoisomeTs of I. 3-clubromo-2-rnetaylbrutznc
(b) Explan racenisation of optical isomers with suitable example 22. (a) Draw all thc stercoisoincrs of 3¢hloro-2-pETtanc}

20. (a) Whal arc enantiomers° Write down their main claracteristics CH,CHONCHCICH,CH,
(b) A compound CH,0 shows optical activity Write down the possible stercoisomers. (b) Give the stereochemical rclatonships of the stereossomers

(c)Opricai activty of a moiecuic s lanked with the prescnce of asymmetric carbon atom. Justiflythe (PTU, 20!0
23 Thefollowing compoundsarc optcaly acave or otËxpian
statcucnt with a suitable Cxample b). -Drcarboxsisprocvciohrptun
(a) I. 3-Diphcnyl propadiene
11 a) What is optucal actuvity? Give the sterco isomcrs
oftartaric acid. How do you account for the 24. (a) What will happenif onc of the OtH groups of tartars acd is replacod by NB, gzop
lack of optical activity in mcso formi and racenic form?
(b) Give examples of optically actve copounds w:thoud chiral
(b) Which of the following compound can exhibil optical actuvity
nclccule aptiealy
(9 CH,CH(OH)CH,CH, (G)CH,-CH, C0OH (ui)CH,C1-CH,Br 25 (a) Does the presence of two chiraB eabon atoms always ak the actve

12 (a)
Explain
Diffctence bctwCCn the icrnus cofiguratuon and conformation.
(b) Dcfinc the tcrm Enantiomcrs. Diasieronmers and mcso counpounds giving examples for cach
(b) Docs the absenceof chiral catbon atoms, always make a meslecnle opt:caily nact e Expha
of them
oBe 26 ) Asign R or S cofiguration to cah ofthe folowitg

13 (a) What is COOH

the nccessary and sufficicnt condition for compound to show enantiomerism?
a

(b) Explan uccessary and suflicicnt condition for optical activity (a) H -OH (b C l ( - h
14 (a) Explain the temu mcso fom with a suutable exampic CH, CH
(b) How can you
determne configuration of gcomctncal isomcts by i) Discu5s stereocbemistry ol kartaric cid
(i) Formation of
cyclic compounds () Dipole mameat
(11) Converting immo oplical somcrs
15.(a) WIal are trausition and iuncr fansition elements? Given an
cleciroic conf1guration Why thcse cleucnts form cxample of cach along with s
complexes?