;Jlc.,t.CV .._ r,L.J • ••-' ' ' '' • . . .

but diITerent arrangements of their aroms in space, i.e., different configuration, are known asstereoisomers
'- and the study of stereoisomers and their properti es is known as stereochemistry. The prefix ' stereo'
means ' three-dimensio nal' , so stereochemistry is also known as 3D Chemistry.
In this chapter, we shall deal with diffe rent types of structura l as well as stereoisomers oforganic
compounds.
Stereochemistry
In organic chemistry we find numerous organic compounds having same molecular formula but
differin g in their phys ica l and chemica l propert ies. Such compounds are called isomers and the
phenomenon is known as isomerism.
As different compounds possess the same molecular formula, the difference in their physical
and chemical properties is attributed to different spatial arrangement of the molecul es.
·An ox"'n.s,on of tho thoory of asymmotry without being a direct consequence of if- for the conviction There are two main types of isomerism, as given below:
the/ rhe geometncal structure of the molecule even for optical isomers exercise such a great influence
(i) Structural isomerism, and (ii) Stereoisomerism
on /he coomJCal affimt,es and could be gained by new actual observations."
\,/°U) Structural Isomerism: It is due to di fferent arrangements of atoms within the molecule.
-Emil Fischer Structural isomerism is further di vided into:
(a) Chain isomerism (b) Position isomerism
(c) Functional isomeri sm (d) Metameri sm and
CHAPTER OUTLINE
/ (e) Tautomerism
101 lntrodudHYi
10.7 Planar Representation of Three Dimensional \.,/(ii) Stereoisomerism : It is due to difference in the arrangement of atoms around the carbon atom
10 2 lsomtrism Formulae: (Fischer Projection Formulae) in space. Stereoisomers have the same molecular as well as structural formulae but possess
10 3 Strvclural Isomerism 10 8 Meso Compounds different spati al arrangements of atoms in space (3 D geometry ), i.e.. confi gurati on. It is also
10.~ Ste=,somensm 10 9 Configurati on on the Basis of R and S Notations known as space-isomerism. It is class ified as:
10 5 Concept of Chiratity 10 1O Specifica tion of Configuration (a) Geometrical or Cis-trans isomerism,
10 6 Types or Op!Jcal lsorners
(b) Optical isomeri sm and
(c) Conformati onal iso merism
Various types of isomerism have bee n summarised below :
filll_ INTRODUCT ION
ISOMERISM
/ 71ic Sten•oc/1e111i,tr, , is the xtudy cf three dimensional configuralion o/ //, e a101ns Iha! make up
mol<'rnles and the ll't11'S i11 11•/,ic/1 the arrangement affects 1/,e phy.l'ical and chemical properties of a Structural isomerism
111111,·c,,!e Stereo or Space isomerism
(S tructura l isomers have (stereomers have the same structure
Onr of the major prob k·ms in orga nic chemistry is to fin d out how the atoms are arranged in different strncture fo rmul ae formul a but different configurations
i.e. , diffe rent arrangements of atoms i.e., di fferent arrangements of atoms
molecules, i. e.. tn d..:1 crm ine th e structu re uf organic compounds. Each different arrangement of atoms
within the molec ul e) or groups in space)
corresponds to a diffr rcnl i;ompound and each compound has its own charac teri stic set of chemica l and
I
pliys irn l properti es. There: is definite ly a relati onship be tween the molec ular stru cture, i.e., arrangement
of :Jto,ns or gro11 ps of atoms in a molecule and its properti es.
Compoun ds which have th e same molcculM fo rmu la, but different stru ctural fo rmul a are called
•
Chain or
Nuclear

+
Position
isomerism

+ +
Functional Metamerism Tautomerism
isomerism
+
1:ro111er s aud lhe compo11nds havi ng different configurati on, i.e, diffcn:nt rdati vc position of atoms or isomerism .. Conformational
groups in space arc ca lled s/ereoi:\'(Jmer r. fn other words, the mok culcs tha l have sam e atom ic con nccti vi ly, Geometrical Optical
iso merism isomerism isomerism
~ ■ A 1 L\'T8'.~
STRUC TURAL ISOME RISM

'-.V c.. ,~ , l.l""' ' '· ' - r,L " "UJ•• ~·

(,1) C bsin lsom<'ris m: Thi;. is ,foe 10 tht' differenc
e in th.: nature o ~carbon chai n. For exampl e,
~

(iv) o-, m- and p- Dichlorobenzene s also show position isomeris

m:
!,TERf:(.}l..r1CIYl1.J 1 , -.. •
-
¢
Cl Cl
s0-penta ne and neo-pentane.
Prot= (CJ~,_, l c-u,ts in lhn."<' i;:onwric t,,nns. ,i z. . 11-pentane. 1
(1 l
CH -C~ - CJ-4-C H 2 - CH,
CH.,----CH-
I

CH 3
CH,-
. CH,. ,
- I
I
CH ,- C -CH 3

© [ Cl
©le, Cl
3 p-Dichloro bcnzc-nc
_ U\.IU'
r,~ CH 3 o- Dic hloro m-Dichl oro benzene
CH, I , 2-Dic hl oro benzene I. 3-Dichl oro benzene I, 4-Dichloro benzene
l<o-pcn rn nc (~-me1 hyl bu ta ne) nco-pc ntnnc
pcntnn<' (c) Functional Isomerism: This is shown by compoun
ds having same molecular formula but
different fun ctional groups. e.g ..
Bury) chlori de ( CJH 0 CI) exists in chain isomers as 11-buty l
chl orid e and isobuty l chloride : Molecular Formula
(11)
CH, CH 3 - 0 -CH 3
I . (i) Cl-1 3 -Cl-1 2 - 0H Cl l-160
Elhnnol Dime thy l ether
CHJ-C H- CH:CI
Cfi:iCHzCHgC Hz -Cl CH 3 - CO-C H 3 C3 H6 0
n-&l)·I c:hlon de fl-chlorob utrul~) lsob uiy l chl uridc (ii) CH 3 - CH 2CHO
( 1-<:hloro. 2-mcth y l p ropa ne) Propi ona ldehydc /\ ccto nc
(iii) CH 3CH 2 COOH CH 3COOCH 3 C; l-1602
( 111) Bur:- Jene (C,HsJ has the following rwo chain isomers : Propio n1c uc uJ Mc 1hyl acc l.1lc
~
TH-' ( iv) CH 3C '=' N Cl-1 3- N ~ C H 3CCN
CHJCH2 CH =CHz CH 3-C = CH 1 Methyl cyanide Methy l isocya nidc
u-Butylen e I But.cl'le-- l l !so bu ry fene ( 2 m c tby f propcnc) 1-1
occupie d by an atom or a I C2 H7N
(b ) Position Iso merism : This is due to the difference in the position (v) CH 3CH 2 NH 2 Cl-1 3- N-Cl-1 3
fw1c1ion aJ gro up in a carbon chain. e.g .. Ethylami nc Dimcth ylam ine
(i) ButanoJ (C., H 9 0 H ) exists as two-pos ition isomers
as under:
(d) Mctamcrism: This isomeris m is shown by the compow
ids having the same molecular fonnul a
attached to the same functional
CH 3-CH 2- CH -CH 3 and even the same fun ctional group. but the two alkyl groups
Cif:iCH3 - CH 2 - CHzOH series, e.g.,
Bu t.a.n ol-1
I group are di fferent. These isomers belong to same homologous
OH CH 3 - 0 - C 3 H 7
Butanol-2 (i) C 2 H 5 - 0 -C 2 H 5
Mt lhyl , ro pyl clhcr
Di me thyl ethe r
(ii) Bu tene exists in 1he fo rm of two-p ositi on isomers
as under:
C l-1 3 -CO- C 3H 7
"<~ (ii) C 2 l-l 5 - CO-C 2 H 5
CH~- CJ-4 - CH = CH 2 CH_
3
- CH = CH - CH 3 Dic:thyl k~tont:
Methyl pro pyl k:ctonc
HulC"n e- 1 But= e-2
C,l-ls CH,CH: C l-11......_ N- H
(iii ) J, 1-Dich/o ro eth ane and I. 2-Dichloro eth ane
are pos ition isomers : (iii) - ......__ N- 1-1
C2Hs,..,.... CH{"
CH, CICH 2 CJ Dict hy lnm inc Me th yl propy laminc
Cff1CHCJ2
and arises due to l , 3 migrati on
l, l -Dicb/oro ch loride l , 2-Dich /uro •·lhun u (e ) Tautom cris m: It is a spec ial case of functional isomeri sms
ur Ethylene chlvrirl e ) with the rearrangement
or Etliylid ino ch lryndc
ofa proton from a carbon atom to another atom (oxygen or nitrogen
the chl orine a tom changes and the phenomenon is called
The positi on o f th e alcoho lic group, C= C do uble bond, and of ca rbon-ca rbon sing le und double bond called ta lllo mer s
fro m lirsr ca rbon atom to the second in all th c cases. /a 11/0 111er is111.
- I A T ()(T0OOK OP ENGINEERi>IG C 11EMISTllY
Further, t: uiorncric forms also ex ist in equilibrium with each other, the stable isomer being
1
in large u111ount and less stable isomer b~mg 111 small amount. For example
(i) Acctalclchyde and vinyl alcohol arc tautomcrs of each other. Acctaldchyde being more
stable isomer is in large amount as compared to vinyl alcohol. Since one of the isomer~

~ . 1 Optical Isomerism

:Jl l: I \L.V '-1''-' ~, ,_.,, .,

It has been observed that certa in compounds resemble on,: another in their chemical properties
as well as in most of their physical properties but they diffc r in thi:ir behaviour towards the action of
plane pulari.1·ed lif,{ht Such compounds arc called optically active and 1his phenomenon is ca lled optical
activity Compounds , which rotate the plane polarised light towards the right arc said to be dextro-rototury

- ----
0
and arc represented as d or ( + ) forrn, where as those which rotate it to 1he Jell arc called laevo-rotatnry
. II
i e.. acctaldehydc contams a kelo group (- C- ) and the other, i.e. , vinyl alcohol contain~ represented as I or (- ) form. These isomers arc said to show optical isomerism. Before proceeding
furth er, it is important to understand the lcrms polarised light and opt'ical activity.
0
II Polari., cd Light: An ordinary ray of light consists of electromagnetic waves and its vibra tions
an cnoli c group (= C- 01-1/, thi s type of tautomerism is also ca lled kcto-cnnl ta king place in all planes perpendicular to the di rection in which it travels. lv/r,11oc/1ru111atic light, on the
tautomcrism. other hand, consists of waves of on~ wave length . Even such a ray ha.s its vibrations in all the planes.
When if a ray of monochromatic light is pa.ssecl through a Nicol prism, the wave mor ion of
H H H emergent light is restricted 10 only one plane. Such a beam of lighl which has vibra11011 only in unc
I I I plane is cal led plane polarized light or unidirectional light. The Nicol prism used to obtain r iane polarized
Cl-1 3- C= O ~ 1-1- C=C- O- H
light is called a polari::er (Fig. 10.1).
(i1) Similarly. acctoacctic ester also shows kcto enol tautomcrism; kcto form being major
product and cnolic fom1 being minor product i (JI<\.~
H OH • • \\\
II I
____,, Cl-1 -C- OrLlinury Nicol Plane An Op11cally (PolamcJ L1g}u )
CH1- C- CH2- COOC2H1 ~ 3
CH- COOC2Hi L1i;h1 Pnm., Polan~cd Ac11vc Plane Plane
(kclo form) (cnolic fonn) L1gh1 Sul,<;J./IIlcc Rotated Ro1a1cJ
Tc,wJnt-. ro•~·ard.'i
R1gh1 Len
(iii) Normal and i\ ci-forms of nitro methane arc tautome rs
Fig. 10.1 Polanzat1on of lighl
H H
I o I / optical Activity: When the plane polanzed light is allowed to foll on another Nico l prism with
H- C- N~
I '-o ----
____,, H--C=N~O--H
' •o its ax is parallel to the first Nicol prism. the plane polarized light passes thought it wi thout undergoing
any deviation. The first Nico l prism is known as polori:.er aml the scrnnd Nicol prism is known as
H
(Numial Form) analyzer If the a.x is of analyzer is kept at right angle to polarizer complete darkness appears due lo Iota I
ffiltJH•.:~ -.:•:." I' .17'"N r
(Aci Forni)
internal reflection (Fig. I0.2).
The compounds showing tautomerism give reactions of the functional groups present in each
tautomer, i.r!., reactions of both the functional groups. The two tautomers can be separated by spec ial
methods and can be kept in separate forms only under special conditions. Under ordinary cond itions
tautomers cxisl in equilibrium with each oth~r.
:::::::::::::::: . 7
.·· 'ir5
F,m Nicol :~:P'.:~.'.:>: / Second Nicol •· Ey e
STEREOISOMERISM Light Pnsm Active Pn!'l m
Source [ Polariser) Subsiancc ( ,\nal yscr)
The isomerism which arises due to difference in the arro11geme111 of atnms in space is called Fig. 10.2 Representation of polann·eter (the dotted lines indicate the angle of rotation)
stereoisomerism. The isomers which have the same molecular structure but different relative arrangements
of atoms or groups in space. i.e.. different conf,gurotion are called stereo isomers and the phenomenon The arrangement of polarizer and analyzer with their axis perpendicular to each other is used to
is called stercoisomerism. There are three types of stereoisomerism: study the behaviour of solutions of organic compound towards plane polarized light. For this purpose a
(a) Optical isomerism (b) Geometrical isomerism polarimeter tube containing solution of organ ic compound is placed between the two Nico l prisms. If
(c) Confom1ational isomerism.
some light appears, it indicates that organic compound has rotated plane polarized light through a certain
angle. Such compounds which can rotate the plane polari::.ed light through o certain angle are known as
optical(\/ active compound1. The property by virtue of which the organic compounds can rotate the
plane polarized light is known as optical activity.
j
lllaa ■ J-\ lcAID"l,A.,'"...,. - -· -
The angle through which plane polarized light is rotated by an optically active compound is ~
-,\
known as angle ofrotation. It can be represented by alpha (a) and it can be determined with the help of 1
an instrument called Polarimeter.
The angle ofrotation depends upon the following factors:
(1) Nature of the compound
(iii) Concentration of solution
(ii) Nature of Solvent
(iv) Wavelength oflight used
(v) Length of the solution column through which the light passes
(vi) Temperature

No plan of
Symmetry
Object
I I
Non-Swnperimpos:ible
lmage
Fig. 10.3 Chiral structure
The rotatory power of a given solution is usually expressed as specific rotation, which can be
defined as the angle of rotation (a) produced by one decimetre length of solution having one gram of
the substance per millilitre. The measurement of rotation is carried out at temperature Tusing sodium
Achiral Structures
A stmcture or object which has a plane ofsymmetry and is superimposable on its mirror image
light (the D lines).
is known as achiral (or symmetrical). A line of symmetry is a plane, real or imaginary, which divides a
.fi . I00x observed angle of rotation 8 structure or an object into two equal halves so that one half is the mirror image of the other half. For
Spec1 c rotation = - - ------..---=---:-------~
L th f d · [grams
of substances present]
eng O ecimeters x in 100 mL of solution
example, the lener A represents achiral structures. It can be easily seen that each of these has a plane of
symmetry and is superimposable on its mirror image (Fig. I0.4).
too xa Minor
or [a ]o= /xC
The specific rotation of a compound is \\linen as [a][ = X0 where X0 is the rotation in degree
at T° temperature. For example, [alft' = - 20° means that a specific rotation of- 20° is obtained at 20°C
of temperature and using wavelength of sodium line (5893 A). Molecular rotation is the product of
specific rotation and molecular mass.
A AIA
Dottt:d line: n:prcscnts
pl, ne of symmetry
ObJC'C t
Superimposab lc
Image
✓- CONCEPT OF CHIRALITY Fig. 10.4 Achiral structure
Similarly, many molecules such as those of methane and carbon tetrachloride are symmetrical in
Chiral Structures
nature.
A stroc111re or object is said to be chiral (or disymmetric) if ir has no plane of symmerry and is Two objects are said to be superimposable if when placed one upon the other. their corresponding
not superimposable on irs mirror image. The most perfect example of a chiral object is human hand. It parts lie on each other. Two objects that are like mirror images of each other may be either superimposable
does not have any plane of symmetry and cannot be superimposed on its mirror image. If you hold your or non-superimposable. For example. two note books of the same size having mirror image relationship
left band upto a mirror, the image looks like a right hand but if you try to superimpose one hand over the ar/erimposable.
other (both palms down), you can not do it (Fig. I 0.3). Similarly a right handed glove and a left handed
glove are chiral objects. \._,/Chirality in Organic Compounds
,4.,
Most of the organic compounds are chi ral in Mirror
The term 'chiral ', based upon the Greek word cheir (which means hand) was first introduced by
nature due to the presence of at least one chiral carbon b
Calm, Ingold and Prelog in 1964. Thus chirality means ' handedness", i.e., the relationship which exists b
or chiral centre in the molecule. Previously a chiral
between the left and right hands, In recent years. the terms chiral and chirality have almost completely carbon atom was referred to asymmetric carbon. A
replaced the old terms disymmetric and dis.1ymmetry respectively. chiral carbon or chiral centre is a carbon atom
Many organic molecules such as lactic aci d [CH 3CH(OH )COOH] and 2-chlorobutane which is bo11ded ro four different monovalent atoms •~'
[CH3CHCICH2CH3] represent chiral structures. The substances having chiral srructures are said to or groups such as Cafx:d . There can be two different
possess the property of chira/ity and these subsrances are optically active. tetrahedral models for C afx:d which differ in the spatial
arrangements of various groups anached to carbon Fig. 10.5 Non-superimposable mirror image
as shown in Fig. I 0.5. models of chiral C atom.
__,I
~ ■" lc.AIUV V ~ V • .._ , .. .._. .. . ........ , ._, _,,.._,.,. ., ,,~ ,
.... ~
Each of the two models is rdated lo the other like an object 10 its mirror image and one cannot be
superimposed on the! other. Each of these models. therefore. represents a chiral structure. j ll may be seen by molecu lar models that chirality in 2, 3-pentad ienc arises due to Lhc fact that the
two groups singly bound to one of the end carbon atoms ofallene system arc in a different plane Lhan
the two groups si ngly bound to the other end carbon of the a Ilene system
~
Similarly we can have two non-superimposablc mirror image stnicturcs for any known compound
containing a chiral carbon or chirnl centre. For example. lactic acid [CH, •CH(OH)COOHl is a chiral
molecule sinc.e it contains a chiral carbon marked as(*) !Fig. 8.61. · ~ TYPES OF OPTICAL ISOMERS
Mirror Mirror The optically active compounds always exist in two or more isomerk forms, and differ wilh
"YOH--q=
COOH COOH COO H COOH respect to their optical acti vity. As already stated, the isomers which resemble one another in their
I I chemica l reactions and most of lhe physical properties but differ in their behaviour towards polarised
H- C•- OH HO-C*- H HO 1-1 light are ca lled optical isomers and Lhe phenomenon is known as optical isomeris m.
I I There are two main types of optical isomerism. These are:
CH1 CH,
Cl-1 1 (1) Enantiomerism (ii) Dias1ereomerism.
CH3
(J)-Planor stn,crure (b) Tetrahedral structure
y.1 Enantiomerism
Fig. 10.6 Non-superimposable mirror images: Lactic acid In 1948, Pasteur observed that an aqueous solution of sodium ammoniWTI tartarale was fou nd to
be optically active. He separated two distinct types of crystals from the solution of this compound and
It must be emphasized, however. Lhat certain molecules may contain more than one chiral found that each of crystal possessed optical acti vity equal in magnitude but opposite in its sign. The
centre and still Lhey may be achiral or non-dissymmetric. For instance, 2, 3-dichlorobutane, shape of the two types of crystals was found to different and they were non-superimposable.
CH3- *CHCl-*CHCI-CH 3• which has two chiral centres (those marked*) exists in many isomeric
forms one of which is not chiral because ii has a plane of symmetry as shown below: Such isomers whose molecular structures are non-superimposable mirror images of each other
and which rotate Lhe plane-polarised light equal ly but in opposite directions are known as cnnntiomcrs
or cnnntiomorphs. The phenomenon of object and its mirror-image isomerism is ca lled cnantiomerism.
~
I
Since the object and its mirror-image isomers differ only in the spatial arrangement of atoms Lhese
+
H- C - CI enanliomerism is only a particular type of stereoisomerism.
The existence of object and its mirror-image isomers was j ustified by Van 't Hoff on the basis of
;;:,:;ry tetrahedral concept of carbon atom. Tetrahedral models of an imaginary compound of the type Cab«/ has
already been shown and Lhal of tartaric acid wi ll be shown in next article. These models represent two
H- C - CI enantiomers of the compound.
I Similarly, we can constnict models of enanliomeric forms of[CHF H(OH)COOHl and 2-methyl-
~ 1-butanol [C 2H5CH(CH) CHpHJ, (Fig. 10.8), which is also known lo exhib il e11a11tiomer i.1111.
n:l
On the olher hand, we have certain molecules that are chiral even Lhough they do not contain any Mirror
chiral carbon. Allenes (RCH =C =CHR) represent a well known class of such compounds as illustrated
Ci"l5
below:
H~ CH,OH HOH2C ~ H
H
Hf ' /
"-c =
Fig. 10.7

C=C
/
~ CH

H
J
Non- superimposable mirror image of 2, 3-penladiene
I CH /

H "-._
J

C=C= /
C
"-

H
H3C
CH1
Fig. 10.8 Enantiomeric forms of 2-methyl-1 -butanol.

Cl-Ii
We find that it is possible to construct two models which are non-superimposable mirror images
of each other and as such they represent the different enantiomers.
 - , , A Tr"~""',..,~-•~' (~.,""~·
\t ll'""l
..., ~ ~,....nlt'II
· .
,;,t, l\1""1'"t-., ~ c11111n1n·
!h.il lilt cu,,l(':11~ M 1t1,1~t tif the C\1mn.1und·
teU'tlhl'11·.I A'l~-lltftfft art1 ,~.r,-Nt ,"111 IN"lf m1m>11mA!,r("~ a~ 1llu~1tatf1.I hdow with th
•·· :111- - ~lsnn'• DI 1
'►l•. ~
ll a (/~) Whrn c•,111al q11cmtltle,, nf e11anliomeu an mu:ed tnxe1hu {t rt,rtJlt., In the (ormullon of ur,
or riptlc:al~v inarl/ve /ontt culled racemlc modinution or r■cemit misran or racem.11tt. The
~
11>..Jtl• 1>f ~,--til(,r("""lhlll'I( l fltq. ~'"~ -~'14.1® .-1<1 not ~xh,t,it cnantiomcri~m help
'"'"' ,,..~~-.,~ 11tt o.l \tic 1-'f'C nuse all rnccmic modification i! dlstingui5hed by wing the prefix(±) bcf~ the name of the compowu.L
For c~nmplc, if C{!Unl qu11n1i1ie, or( ~) lac1ic acid and (- ) lactic acid~ mixed with ea,h
M111\V other, we get mccmic or(±} lactic acid which is optically inactive.
(.,
1.ANAR REPRESENTATION OF THREE DIMENSIONAL FORMULAE:
'\.., FISCHER PROJECTION FORMULAE
H--l)-H H~ H
It is not wry convenient lo represent the formulae of stereo-compounds oo papa-. A ..simple.
/ Br method was introduced by Emil FiJcber ( 1891) for projecting lhn:e dimensional formulae of chiral
tit molecules on planar surface. The planar represenlalions arc called F't,cber projection formu!M.
,..7 The following procedure is adopted for writing the projection formulae:
<•""rial COftdition for ENntiom•rism (i) The chiral molecule is considered lo be so held ti,at two groups attached to chiral carboo lie
V !Onanballl!l1( _ _ . ~ ahl·a~'5 IIOll-surmmro,uble mirror images of each other. The horizontally and point lowards lhe observer while the other two groups lie vertically and
~ . _ . , ,,...,....,..lffl....t,l,l m,sadur 10chiral nature of the molecules.A molecule point away from the observer.
•,,,...,.;.,. ,.,.,,; if 11 , _ ,.. , , : - .,r ~~- awl i.s, thcre_lort. 11011-superimpoJable 011 its mirror
1· ,,,,. (ii) The various groups atlached lo lhe chiral carbon are then projected to the plane of the paper
so that horizontal lines represent bonds pointing towards the observer while vertical lines
a..lil)- ■ --olrk ~ ll'IC'llecules i1 itsclf due to the presence of at least one chiral n:pn:sent bonds pointing away from 1he observer. In case the chiral molecule coniains nvo or
~ ■ tw ....._ .Far Cllllllfllc, IKbe acicl ICH/CH(OH)COOHI and 2-mcthyl-t-butnnol mon: chiral carbons, each carbon is considered separately as described above.
f('.H.~,l{'HpH] . . . . ..: daral carlltwl each (the one marked•) and therefore exist as (iii) The vertical part of the projection formula should represent, so fat as possible. the longest
- • • • ..._ • ....,.~. Oii dlr acherhand. there can he molecules such as 2, 3-pcntadiene chain ofcarbon atoms in the molecule with the carbon atom to be numbered as I ai;cording IO
-
...,_ • • _
11-., 11r
~

_, ....i canai bal lbc)- llill poacu lhc propcny of chirnlity and thus exhibit
I o t, ~ 1hr dura&r) (u., the propcny ofeitisting u
- . ..... • •.:b 1 .,. .,J Cllllt·&.ved111un ,,fenarrr,omerislfl.
non-superimposable

IUPAC system being written at the top.

For instance, the projection formulae of the two enantiomers oflactic acid may be represented
as shown below.
COOH COOH
I
01 C rllfica f1I En■Dtioa-- I
1'11t . . . . ..-w-... ol thl' manumnen of a given su!,stance are described below:
H-C-OH
I
HO-C- H
I
CH1
t#l n.,..., ...,._"""'"" ,,,_,,,,.,. such u melting points, boiling poin1s, densities, CHJ
......_ lletrat'tivr iodiuta. The only difTc~ce lies in the direction on of ro1atlon of plane (R)-Lactic Acid (S}.[.xbCAcid
,....._, lapc. •khoueh the fllqllllude of specific l'OOllion is the same. (iv) Very often the chiral carbon alom is not written at all while writing the COOH
,._. nc,, "-'"' "'1elk.t ~ ~ n acepr in .reactions with olher optically active projection fornmlae. It is lalcen for grnnled that the chiral carbon is located
-,..unck. hr r.umplt, the Oldtnary chnrucal reactions of(+) lactic acid are exactly like where the lines showing the horizontal and vertical bonds cro.'IS as !lbown H*OH
__ , ol' 1-1 l.c-lJc llfJd. ~ ma~• be- 11 d,lfcrence, however, in the rates of reactions at which below. C CH1
• Ollll&Uuma, l"QCI with Mnnr other op11,·,ill)' •ctive compound. For instance, the rate of (v) If nece.v,wry, planar for11111/a 111<1y b<' imuginc:,I ro be rvratt'd.from t'n,/ tu errd bu, without
__,b.iun of(• I lactic aid with(•) liCC. butyl alcohol fCH.1CH CH(OH)CH ] would be lifting it/mm the plune ofthe part!r. Rotation by 180° in the: plane of the papa does not bring
2 3
dtft'WClll lroa, 1hr ~uf e11cr,th:111iucl of(--) IMCtic acid with the same alcohol. about any change of conliguralion. For example:
viii 'llwy ~•16,,_~~ ln oonunt to physical and usual chemical properti~ ,
~ arc qwtt dtffmnt in llwir biological properties. fo, example, (+)sugar plays an
111 H- ~ Otl
COOH
Ru1at1\,11
HO
+ COOH'
rI
......._ f'lllc animal UIINboltStll wh«r•s I· ) i;ugu is not mclabolized at all. Similarly, ·nuuutb 1.w > H
(•) tanarie acid LI rt'edily llUIIIIUmed by dw mould pcnicilliwn glu11cum while H tartaric
1dd11noc. n1_, CH, i
t( - ) La11c ooiJ 11~- ) Laue ac,J
I (No change In configurallon: I ond II represent lhe same. compound)
__ j
 EU I A TEXTBOOK OF t NGINtlN.IN~• "'- ' II· •· ..... .. ~.
But rotation by <J0° or 270° kads to in version ofconfig11ration (i.e.. changes o ne configurat io
1111,, its min or inngc) so that the new con tig11rn1ion represents the cnant iomcr o f the o rigin,:;
Exam ination of formu lae I and II reveals that they are non-superimposable mi rror images of
....
each other and hence represent a pa ir of enantiomers. Simi larly Ill and rv are also nori-superimposable
comp011nd. mi rror images of each other and as such represent another pair of enantiomers.
H Compare the fom1ula I with fonnu la Il l.
COOH
f.:.,,rn11l'.'n ➔
CH, + COO II CH3
C H1
H+ OH
CH ;
Thr.,u~h t)O"'
OH I, S:.imc
Conligu rJlion H-C-
I, CI
I\'(- ) LnLl 1l' :ic1d
H- C - C I
111 (-) LlCIIClCld
3 3
(1·i) If positions of two g:roups or atoms about the chiral carbon are inte rchanged it also leads to CI -C - H Mirror Image H- - C- -CI
inversion of conlig11rati,,n. But if we carry out two such inte rchanges. the configuration I Configuration I
C, H5 C,Hi
remains una ltered. Ill
COO H COOi-i 1
COOH It is clear that the two formulae have identical con figurations about one chiral carbon (C ) and
f ire;!
Sn:-..:ind the mirror image con figu rations about the other chiral carbon (C 3 ). The net result is that the two fom1s
HO + H Interchange HO + CH 3 are neither identical nor mirror images of each other. Such stereoisomers of a subsrance which are
H+OH lntcl'('~an~c
H neither mirror images of each other are nor superimposable are known as dias tereomers. In addition to
CH3 CH 1
V II(-) Lactic acid formulae I and Ill, formu lae I and IV. II and Il l, II and IV also represent pairs of diastereomers.
\ (- ) L3cu..: ocid VI(• ) L.:ictic aciJ
Im cr-1cin of configurnlion Configura1ion snm e llS 3-Chloro-2-butanol affords another example of a compound having 2 dissimilar chiral carbon
tlrnt of I
atoms and can ex ist in fou r stereoisomer fom1s as given be low:
It is quite e,·ident from abo,·e that one interchange is equivalent to rotation by 90° o r 270° wh ile
CH, C H3 CH 1 CH3
No interc.hanges are equivalent to rotation by 180°. I . I I I
HO- C- H H- C- OH HO- C-H
XO.7 .1 Dias tereomerism: Compounds having More than One Chiral Carbon H- C-
I
OH
I I I
J .- We ha,e learnt that a compound contain ing one chiral centre exists in two ste reoisome ric fom1s CI- C- H H -C - CI H- C - CI CI - C- H
which are J...,iown as enamiomers of each other. But compounds containing more than one chira l centre
~
I I I I
can exist in more than two stereoisomeric forms. To il lustrate this statement, let us consider the case of CH1 CH 3 CH3 CH3
::!. 3-dichloropenL:me: V VI VII VIII
It may be seen that structures V and VII, V a nd VIII, Vl and VU: VI and VIII represent pairs of
CH,-CH ,-CH-CH- CH3 diastere.omers.
. . I I
Cl Cl ,a racteristics o f Diastereome rs
which contains two chiral c.entres. Si nce the four different groups attached to one chira l centre are not The important characteristics of diastereomers arc as fo llows:
the same as those attached to the other. the two chiral carbon atoms are dissimi lar from one ano ther. (i) They show similar, but non identical, chemical properties. In the reactions o f two diastereomers
There are as many as four stereoisomers (I, II. Ill and IV) possible for thi s compo und. with a given reagent. the rates of reactions are generally different.
CH. (ii) They have different physical properties, such as melting points, boiling points, densities,
CH, CH. CH
I, , I, I,, I, J solubilities. refractive indices. Even specific rotations are different: this does not, of course,
H- C- C I CI- C- H 11 - C- CI CI-C-- H apply to diastereomers which are geometrical isomers since such diastereomers arc no t
I, I, I, I, optica lly active.
c1- c·- H H -C-CI H- C - C! c1- c·- H (iii) On account of differences in physical properties, they can be rather easi ly separ.ltcd through
I I I I
C11-1 5 C, H5 frnc tional crystallization, fract ional d isti llation. chromatography, etc.
C2Hi Ci Hs
II Ill IV
Ont" pJ1 r uf en11111orn.:-rs
Sc:1..ont.J pJ1 r ,i f rn.m,iomcr.,
 ,- I
.f

A T EC\,nOOK
-··~·· ..
·-···-·
or ENr.1NHRJNG (HEM1STRY
nd Diastereomers
-:~====-------- spite oftwo chiral centres in it, the molecule is not chiral. This

:)TERt~H~l:)IKI
I

■
COOH

.....
~~
~:::.:.:__:_:_:~_:_::_::::.::_:.:_::__:::___:__ _T _______ is because it has a plane of symmetry; one half of its molecule
l)instercomcrs H -C - OH
'Enantlomrrs being mirror image of the other half. As such the compound
Tl represented by formula XI (or XII) is optically inactive. Such Plane o f - - - - ~ - - ·
,'
~ 1, 1CS\.' :!ill'r\.' 0 l~(' llH.' r!< 1\ .-1\ .... ;\ n 1·,rr ~,r imn,•c
o
I These· ,tcrcoi~omcr,; do not hove n mirror imng:-;
' . ~ ,
r<IJtionsh,p. rcbtionsh1p. 1111 optically inactive compound whose molecules are not chiral Symme,3)' H -C - OH
:c. The,-· have similar ph) sic,il pmpcrt ics, such us ~- Th,·sc hove different physical propcrti~s such ;;;
even though they contain two (or more) chiral centres is known V I
as a 111eso compound. As explained above the molecules of COOH
melting p,1 1111. boiling poull, s'1lub1li1, in :i giwn melting point. bo1hng pomt, solub1hty 111 a given
such compounds are superimposable on their mirror images.
, ol \l·n1. density. ~h.:. sol\'ent, density, etc.
Thus. tartaric acid exists in three fonns: (- ) tartaric acid (fonnula IX). (+) tartaric acid (fonnula X)
3. Thc,e c:innot be scpdr'Jl,·d t,y such methods. 3. These can he sep:1r:-ncJ by fractional distillation~ and meso-tanaric acid (formula XI or XIJ).
frac.tionRI crystalli za tion and adso rpti on
Although optically inactive, the meso-tartaric acid represents a diastereomer of(-) or (+) tartaric
chwrnatography.
acid.
~- The) ha1c optic.nl rotanon in opp<'Slle direct ion 4. They may haw optical rotation in the same ; It should be noted that meso compounds are pennanently inactive and are said to be internally
but to th< ,:m1e e.,1en1. e>pposite directions but to a different extent. compensated i.e. rotation of one half of the molecule cancels the rotation of other half.
5. They ha, c identical chemica.l propenics ncept 5. Thcv have identical chemical properties but differ Number of Possible Stereoisomers in Compounds Containing Different Number
with Nher up1ical l) active compounds. in the rate of reactions wit h opticall y active
compounds. of Chiral Centres
It may be stated that the maximum possible number of stereo isomers of a molecule is 2" when n
is the number of chiral centres in the molecule. Thus the molecules having I, 2 and 3 chiral carbon
,,. MESO COMPOUNDS atoms ex ist in 2, 4 and 8 stereoisomeric fonn s respectively. The number is. of course. less than the
J Consider a compound containing two similar chiral centres, i.e.. having the same set of four
maximum if some of the isomers exist in meso fonn .
different groups Jttached io each of the chiral carbon atoms. A typical example is tartaric acid: 10.8.1 Internal and External Compensation
• CHOHCOOH Internal Compensation
I It has been stated above that meso compounds are optically inactive because their molecules are
*CHOHCOOH
In view of the fact that it has two chiral centres. one may expect the existence of four stereo isomers l not chiral even they contain two (or more) chiral centres. For example. it is clear from the structural
fomrnla of meso-tartaric acid that the top half of the structure
COOH
of this ac id having the confi gurations IX . X, XI and XII. is the mirror image of the bottom half. As such the optical
activity due to one chiral centre is counter balanced by the H - C - OH
I
COOH COOH COOH COOH optical activity due to the other and the compound is optically Plane of
I I I I
H- C - OH HO-C- H H -C-OH HO-C- H inactive. The compensation of optical activity due to one half Symmetry----~---
,\
I I I I of a molecule by the other half is known as internal H- C - OH
HO- C- H H -C- OH H -C-OH HO- C- H ca111pe11satio11 and the molecule is said to be intemally I
I I I I compe11sated. An internally compensated molecu le is
COOH
COOH COOH COOH . COOH perma11e11tly inactive.
IX X XI XII
PoJJ r o f' 1.'T!tan11omt>rs External Compensation
Supcrimpos:tbl~ mirror imogcs
rcpr.:!ll'.nt only one compound In a racemic mixture equirnolar mixmre of two enantiomers, say (+ ) and (-) lactic acids are
Formulae IX and X are non-supcrimposabk mi rror images of each other and, therefore, represent present. The molecules of one enantiomer would be present in a quantity equal to those of the other
a pair of optica lly acti ve enanliomers. enantiomer. This means that rotation of plane polarised light by each isomer would be equal in magnitude
Fom1ulac XJ and Xll again have a mirror image relationship. Close exam ination of these formu lae, and opposite in sign i.e. direction. Therefore, exact ca11cellation of all rotation would take place and the
shows that one of these structures may be superimposed on the other just by rotati ng ii through 180° equimolar mixture would be optically inactive. The cancellation of rotation of one e11antiomer by the
within the plane of the paper. These two fonnu lae, therefore, represent two superimposable mirror other iu an equimolar m frture of the two enantiomers is known as exter11al compensation a11d the
image molecules of the same compound. F11rrher examinatir11·1 off,m,11,/0 XI {ur XII) re ,·euls 1/,,11 ill .• racemic mix111re is said 10 be extemal(v co111pe11sated.
Ill'. ~•· ::::;,. µJ£CP ;:;z:z:sz ·~•·• )
 ~ -., ... , ............... ~.
It ni~~ ht' r-•i nl,'<I , :,.,: ,t 1hr l" •' ,. 11 ,1111 1,,,.,n, .,re 111 1! n u \l'd 111 <'qlli111nl n1 qu ,11Hil il',, lhl' lh c re lati ve pri o ri11 cs ofC H a nd C H a re decided as foll ow s. Ea c h of the se g roups is linked
1 111 1 1 2 5
rt• lt1l1011 ~;l\ M ' d t,> ,, ,, ,, ,., 11,•llk'l , wt .- , ,1-ii , , ~11,..:llnl t,, till' ,,thcr. 1\ ~ Sll Ch lh is 111 ix lllrc s1i1t In the c hiral ce n tre through the sam e a 1o m . i.e.• carbo n. T he n ex-1 a to ms in C H 1 are 1-1. Hand
11 11 1 1 1
c,h,t-11 , , ,,rnc ,,,,1 1~!\ll) ,..-1, , 11\ I he dm.'< 111,11 ,,1 ,.,,, ., ti<•ll ,,,m•,r(llld, 1,, 1h01 of 1hc c111111ti11111 e r prc•se 111 1-1 w hik in C / 1 they are C. H and H. S in ce carbo n has a higha a1o mi c number th an hydrogen .
5
l.111: rr l]U!\11111;, t•u1 th,
II\ ,,,,-tfk
,,,1,11 1,•ll ,, k,,,.,.l 111h,, "·'>
p.1rti~l c,,111rc• 11 ,11 t i,, 11 lnJ.. c s p ln,c 1111d th e C/15 ge ts hi g her pri o rity.
n11 , 1ur.· f11m~l'\J 1.., , .11J t,, t-,: 1>-11i1., tl~ r,1,'\:11\t " ' J ( iii ) l(o gm11p has c111 010111 . \'" l inked f<• sume other orom by dcm hle or 1riple bo nd. Xis cons idered
H
Co m pa ris on o f Exu , rnal and In te rnal Compe nsa tion s I
c,111 i,•ale111 to tw o or three such a/0111s. Fo r ins ta nce, if we co mpa re the H g ro ups, - C = O
ln1 r rntt l Compeo,ntlo n
E1;tc,,..i C'oml)t'ns,oriu11 and -C H~O H. the fo nn er ge ls hig he r priority as the nex t a to m s in it are equiva len1 to 0, 0.
I It ,, 11t1rrl,r- 1111 J g c: rdnti o ns h1p bc t ,"v cc n 1h e 1-1 w hil e in C H 20 H they arc 0 . H. H.
It ,, Tlll fT\..'l· IIH.J t=:\..' 1c-L1IH..'ll 'h!j' l°', l \H' ..:11 lh1..· !
'-lntdtm.> l,1 t,, o hn l\ c-, l--if th t.· i:: nmt· mol C'c ul c. It ma y be noted . ho weve r. tha t ifin a g roup two o r three a 1o m s o f X are s.:parately Linked to some
,tti.h.'1\;.I\'' l'l 1h-c- nll'h.~,u1t, l\l 1,, 1' 1.' ni.1Ulh' l11 "' ' '
11,1\l-J h .., ~\lh l·r. in <."1.IUJl .U1l1."L111 l
1
atom 1h ro ug h s in g le bo nd s , s uc h a group wo uld ge l prio rity ow r th e group con1aining doubl y o r tripl y
- - I
Thi.' m,,h.·•ttUIC"'- l'f <ml". l.'."n..1nlh'mr 1 1...~m,l•J.., 1h1,.• "" l1nl' half o r the ml"'lrnil c cm1111 c r-bolancc s the H C H,
t'.•t.it1,,n Pl ltl~ l'th1.' r c-r-mthiml·r o l the nth er half.
1111 ,ttll·m I I
.._ bo nded X. Fo r exa mple . lei us compar e 1he g roups - C = C H 2 a nd - C H- C H, . In bo th these! gro ups .
lllt" r.1.;c-111.'.l.lt" fom, c-J 1, .1 mL ,nm: ,,it\\.-, '"'m~11 1. ~ email , 1..,,mpcn, otcd com pound o r Mesa form
I .. ,,mrl'lmd, j r.:.-prl~ l'nl " :1 , 111glc pure compound . C H,
I .
~ (\1m plc-1~ \... . r rurt1 .1l l"\ t:mul 1.·\.111,pcn,..1\h'n ,d ..i r ~1r11.1I in 1cm.1I r0111pcn'-n1ion is not possible . the nex t a to ms will be 1ak en as C. C. H . Howeve r, in - C H- C H 3 , 1hc 1wo carbo ns are ac tua ll y a n ac he d
:\•"..Jtwn ;-. l'l\',,11'k
H
:, J: ,~ :in.- , ~1hkph,..:-....... ,.mJthc:r.1 \~1111cm1,1urc i 5 It 1, :, pcnn:111cn1 cfft cl and it is nul possible lo I
throu g h s ingle bonds whil e in - C = C H there is o n ly o ne carbon a 11ached 1hro ug h d o uble bo nd . A s
......m N' n~,h ell 1n 1 , 1 \ \ md \ 11.•nJntu,mcr, r1..•,l1h c nn int c:rn a ll y compc:nsntcd molecu le into 2
0p11call y ac t!\ c fo n11 <.. C H, 1-1
/ I I
'-..;/ rffl CONFIGURATION ON THE BASIS OF R A NDS NOTATIONS
/ suc h the group - C H- C H, gets pri o ri1 y o wr - C = C l-12 •
C:thn. 111~1, ld Jnd Pr,·lng wggesit·d a, er> ,impk rron·d ure lo speeif'y a p:irtic ul nr con fig urat ion
,n tcm JS of rrcfi,c, R o r ~ - Tht' le 11cr R 1, 1.,,en from Rcc1us an d S from S inisler The procedure
Simi la rl y C H
6 5
-(-e.@-) g clS pri o ri ty o ve r - C H = C H - w hic h in tum g e 1s prio rity
1.1.1, (,I, c, the fc,llo \\ mg I\\ 0 s11er~· over -C H = C l-1 2.
Stt>p J. Tl·t..·_f,11n uJr>m , or gruur, of t11, ,111 , hu11dcJ 10 1'11: chiral centre ore o.,·.,·(~111! d a sequent.·e
ufpn"orirjc•\ mu._·, 11r,/cn i:. ,. nllh u \cl v i ru ll·, lu1uwn us ~,equcm_t' rules. Note. The pheny l group ( @-) is considered as i f it has o ne of Kekule strnc n ,re s tha t is :
Sequence Rule s
lhc <,·qucm< rul e< J Jt a:, foll t"" : H
<1 1 If u ll 1/h..· four titurn, tf, ,-,.,uh· a!la c. hu -/ t1> 1he ..,/urul t. L.'lllre are d iffer eur from o ne c111nth1!1~ I
.\( ' f"Llh t of1ir1nr lfli. , tl di.:tt'rrnm, ·cl l11 u tumil n11111her The atom of highest atom ic number H- c ::-C c - 1-1
,•er. the ht t!hc<I rm•111 } whi le the nnc "11h th~ lowcsi a10111ic I II
num be r comes las ! in o rder of H -C~ ✓ C - 1-1
rrinrn >. ro r t·x,lln]}le. ,n Ul t' ru111puu11d 1-hrom»-1 -chloru-cth ane. C H C H( C I) Br. the seque nc.:
3
u l pri<l111ies "d i he llr, l I. L' . 1-1. I
1-1
( 11) lft\\<> »r 111, ,rc ato ms d 1rcl'1 ly 31taLl1cd lu the chira l cen tre ha ve 1he same a1 0 111ic number, the
rt'ia1i,c pr10ri111,s tnay he li ,.ed by c un,r,mng 1h c nc , 1 atnms in 1he g roups . If e ve n lhi s d oes As s uc h the atoms next 10 the carbo n a n ached lo ch iral centre are trea ted as C. C and C .
11<,1 ,,o lvc !h e pro hlem , lhc cn,np,,,·i•,on '" ")' he cx 1cnckd 10 I.he nex t ato m a nd so 011. For Step 2. Aller deciding the scquenc.: o r pri o rities. the molecule is imagined to be in a position
in ,n-but) I .11l.cihn l,
t' ,\,Hllp lC" .
whe r.: lhe group of lowes t prio ri ly is direc1ed awa y from us . Now, we look a t the arrang em.:nt of
II remaining g roups in dec reas in g o rder o r their priorities. If in d o ing so, the eye travels in clockwise
I directi o n , th e co11lig ur,11iun is spccilied as R. {Latin : r<:c!Us= r ig ht). If. on the other ha nd. the .:ye travel s
11 / ' I I .I (' (' If I in un liclockwisc direcliC' n. !he .:o nli g u ra ti,,n is s pecified JS S {L a lin : s ini s ter = ld t ).
I
() ]J
 am • A TEXlllOOK OF ENGIN EERING CHEMISTRY
Above rules arc further explained by considerin g some specific examples:
(/) Lactic ncid, CH 3CH(OHJCOOH.

-
In the ea rli er clays, it was not possible to determine the absolute configurations of the compounds.
Fortunately, it is not always necessary to know the absolute configurati on ofan optically active compound.
The sequence ofpriori1ics is OH . COOf·I. CHy 1-1 . Therefore. 1hc specific confi gurati on may On the other hand, we are more inlcrested in knowing the relati ve configurations of different compounds.
For example, when an opticall y ac ti ve compound undergoes a chemical reaction, we arc mainly interested
be desig1iatcd as:
in whether the co nfigurat ions of the reacta nt and its product are same or different and not in their actual
COO H confi gurati ons.
COOH
f /4elative configurations by D and L Notation
V . 1
It was proposed by Emil Fischer ( 1885 J that a standard reference co111po1111d should be chosen to
assign rel ative configurations 10 various optically ac ti ve compounds. The compound chosen as the
H standard was glyccraldchydc (CHp HCHOHCHO) and its two cnantiomcrs were designated by the
H
symbols D and L. ft must be made clear !hat the symbol D and L refer to configuration and are quite
H3C OH
Cl-1 3 difTcrcnt from th e prefixes d and/ (read as "dextro" and ··Jaevo") whi ch refe r to the direction of rotation.
HO
R s (+)-Glycera ldehyde was arbitrarily assigned the configuration Ill (in wh.ich the - OH group attached to
chiral carbon is towards right ) and was given the symbol D. The (- ) enanti omcr was assigned the
(Ii) Chloroiodomcthune sulphonic acid, CH(Cl)(l)S 30H.
configuration IV (in which th e - OH gro up atlac hed to chiral ca rbon is towards leflJ and was given the
The seq uence of priorities is I, Cl, SO H and H. Therefore, Rand S configurations may be
3
symbol L.
represented as shown below:
Planar Representation
Cl
CHO CHO
I I
H-C-01-1 HO--C- H
I I
CHpH CHPH
H H Ill IV
D-(+ )-Gl yccraldchydc L-(- )-G lycera ldchydc
~,
~
SO 1 H SO 1H
Three Dimensional Representation
R s
CHO
H
-YOH
CHO
fl•'•'•'•'J....:S:....P....:E:...:C:....l.:....F....:IC:..:.A....:T...:.IO-=--N-O_F_C:....O.:....N_F_IG:....U_RA_T_l....:O_N_ _ _ _ _ _ _ _ _ __ _
\.../111
H0---...1. H
The configurations of the 1wo enan1iomers of lactic acid are I and II shown below. One of these
configurntions represents dex tro or(+) aci d while the other represents lacvo or( - ) lacti c acid.
COOH COOH CHpH CHpH
H+ OH HO + H Reasons for selecting glyceraldehyde as the standard
CH_, CHi Glyceraldehyde was chosen on the standard mainly because of the following reasons:
II
(i) It is the sin1plest carbohydrate-an aldotriose its configurati on could be easily related to
Specitication of conligura1ion means wh ich one of the two enantiomers. (+)or (- ), has the 1hose of the other irnportanl carbohydrates .
configuration I and wh.ich has the configuration IT . In 01ha words we do 1101 know the actual or absolute
configuration of each of the 1wo enan1i omers.
.,
 {Ji) Since gly~~ra1dt'hydt~ 1..' l'ntnins \'t' . reac tive fund ionnl groups it could be converted into
0
many 1,.)tlwr typ~s of Ct)mpounds . h\ this way it cC'lltld be confi gurationally related to a large
numh:r l,f 1..'1..'tn\.' l'Unds .

Correlation of Configuratio n
M~u\y OU\l.' r 1..' 1..)lnp0lmds Wt.'\\.' then assigncJ relativt: configw-ations by relating their configuration
to that t"'f D- 1.). r l glytemldebyde For this puJ:l)ose either the compound under examination is converted
inw D- or L l:?-ly~crnh.khyde 1,.,r it is l:01\Yerkd int o the given compotmd by means of reactions which do
1101 im·ol\'t· h1\\1ki11g <f h<111, ls 10 u chiral ct'11tre. T he genera l principle involved in correlatin g the
configarations of t\\''-' compounds is that if a reaction does not involve the breaking of a bond about a
1.'hir~\l c-entn·. tJ,e confignratit)n ab1..mt that chiral centre remai ns unchanged. Some important examples
of the ( Orrel~ti0ns 1..)f the configurations m't' given below:
t1) Configuration of(-) Glyceric Acid: Glyceric (- ) acid can be obtained by the oxidat ion of
D t+)-glycernJdehy de as shown below. Since this reaction does not involve breaking of bonds
~1 bout the chir:11 c1:•ntre. (- )-glyceric acid must have the same configuration as that of
glycc-raldehyde
. taken i.e. D configuration. -
CHO COOH
I Oxid I
H-C-OH H-C-OH
I I
CH,OH CH 2OH
0-(+)-Glyceraldehyde O-(- )-G\yceric acid

(ii) Configuration of(+) Lactic Acid: The configuration of(+) lactic acid was established to be
similar to that of L-(-)-glyceraldeh yde by the following reactions:

CHO COOH
I Ox..i d I P/Br~lPBr)
H- C-OH H- C -OH
I I
CH::OH CH,OH
D-(+)-G Iye era ldehyde O-(- )-G lyceric acid

CHO COOH
I Reduction I
HO- C- H - 1-1 Br HO- C- OH
I I
CH 2Br CH 3
L-(+)-3-Bromo- L-(-+ )-Lactic ac id
2- Hyliroxypropano ic ac id
~ • ~ • ~ • u v vn v• ---~·"--
It must be emphasized that th ere is no direct relationship between absolute confi guration and COOH COOH
direction of rotation of polarised li ght. Two substances may have similar relative confi gurations and yet I I
may rotate the pl ane of light in different direc tions. For example. D-( +)-glyce raldehyde and D-(- ) COOH HO-C-H H-C-OH
glyceric acid have similar confi gurati on even though the fom1er is dextrorotatory-whil e the latter is I I . I
HO-C- H H-C-OH HO-C-H
levorotatory. I I I
C HP H COOH COOH
CHO COOH D-(-J-Tartaric acid L-(+ }-Tanaric acid
L-(+)-Lac lic ac id
I
I
H- C-O H H- C- OH
I I 1 0.1 0.1 Configuration on the Basis of Projection Formulae
CH,OH CH,OH
D-(-)-Gtyccric acid While assigning configuration to a stereoisomer on the basis of projection formula, the procedure
D-1+}-G lymn tdchydc
is essentially the same as in case of three dimensional formulae. However, if the group oflowest priority
Similarly two compounds may have different configurations and even then they may rotate the is pointing towards us (i.e ., bonded horizontally) an additional step is required . In such cases the given
plane of li ght in the same direction. For example. D-(+)-gl yceraldehyde and L-(+)-lactic acid have formula is converted into another projection formula by making two interchanges so that the group or
opposite configurations but the same sign of rotati on. atom of lowest priori ty is placed vertically downwards or upwards. Then the configuration is assigned
COOH following the usual procedure :
CHO
I I
H-C-OH HO-C-OH
I I ~ (
CH,OH CH,OH ( l ) ~H=C H2
/4
D-(T)-Gt) ccraldehydc L-(- )-Lactic acid
ute Configuration
81jvoe1 (/951) was able 10 de1em1111e 1he absolwe co11fig11ra11011 of a compo11nd bv rmng X-ray The sequence of priorities is C l, © - - CH=CH 2, H. Therefore, configuration is S.
diflraclion s111dies. 'The ac/110/ arra11gemen1 in space of !he a/oms or groups cons1i1111ing a parlicular
slereo isomer is called absolure co nfig11ra1ion. The first compound whose absolute configuration was CH 3
CH 3 CH3
determined was sodium rubidium salt of(+)-tartaric acid. Bijvoel confirmed that (+)-tartaric acid acnially First Second
lnterc han gl! Interc hange
has the same configuration, which was previously assumed to have on the basis of configurational (ii) H+OH HO + H HO+CH 2CH 3
relationship between glyceraldehyde and tartaric acid (as described earlier). If the assumed configuration CH,CH 3 C H2CH 3 H
of (+)-tartaric acid was correct, the assumed confi guration of the two enantiomers of glyceraldehyde
must also be correct. As such the configuration of all other compounds derived by correlation with
glyceraldehydes must be correct ones. Thus the relative configuration assigned to D-(- )-glyceric acid, The sequence of pri orities is OH, CH 2CH 3 • CH 3 , H. Therefore, configuration is S.
L-(-)-lactic acid (discussed earlier), carbohydrates and a large number of other compounds acnially
represent their absolute configuration.
The absolute configurations of some simple but stereochemically important compow1ds are given
below in the planar form: (iii)CH 3+ H

CHO
Fi rst
Interchange
--~-►
C
H 3

+
CHO
NH 2

Second
Interchan ge
----
fT4
NH,+ c k
CHO CHO
NH 2 H H
COOH
I I I The sequence of priorities is NH,. CHO. CH 3• H. Therefore. configuration is R.
H-C-OH HO-C- H H-C-OH
I I I
CH,OH CHpH CHzOH
D-( +J-G tyccraldchydc L-(- )-G lyceraldehydc D-/ - )- Lac11c ac id
-
1 0. 10.2 Configuration of Compounds Containing More Than One Chiral Centre
In such cases the conlicmation about each chiral centre is asccna ined separately. TI1c spec ification
Confi guration at 3C can be obtained as follows :
o f eac h atom nlongwith iLs n~mt-c:r is then prefixed be fore the nnrnc of the compounds as illustrated
be low: H__:C- CI

CHCIC H3
,I (/aicJCH
.r •
Cl---!c-CH.
3
m
(i) Let us consida one or the fo nns of tanaric acid . I (After rwo I ,
ln1erchanges)
CH3 H
•C HO HCOOH Configuration = R
I
•CHO HCOO H Hence the configuration of the above compound is (2S, 3R).
Eac h chiral centre Ln this molecule has the same set of four
group, anached to it. The sequence of priorities of these • anw•• GEOMETRICAL ISOMERISM
groups is OH. COOH. CHOH-COOH. H. Following thi s
seq uence of priorities. the configurations around eac h o f th e Geometric isomeri sm is a form of stereoisomerism and is also known as cis-trans isomerism or
chiral centres is S so that the compound may be designated E-Z isomeri sm. It is shown by the molecule which assumes rigid configuration due to hindered rotation
OH
are (~S. 3SHanaric acid . around carbon-carbon double bond. Hindered rotation may exist in C-C single bond and in cyclic
compound .
/~
1vvn \
1 0.11.1 Geometrical Isomerism or Carbon-Carbon Double Bond
This isomerism is mostly shown by such compounds that contain at least one carbon-carbon
H-C-OH HO H double bond and in which each of the doubl y bonded carbon atoms has same or different sets of two
I unlike atoms or groups .
HO--C - H
\
~

I
COOH/
(ii) Let us now assign configurati on 10 the compou nd

V Thus compounds of the type abC = Cab or abC = C:ry show geometrical isomerism .
Due to hindered rotati on around carbon-carbon double bond, the relative positions of the atoms
or groups ·attached to the doubly bonded carbon atom gets fixed in space g iving ri se to two di stinct
isomeric forms. For example. 2-butene. H3 CCH=CHCH 3 can exist in the following two isomeric forms :
H C H3 H C H.
CH 3 ' c/ ' c/ ,
,/ II II
H--.:C--C I / c, C
,I H CH 3 HJ C/ H
H__:C-C I
cis-2-Butene trans-2-Butene
I
CH3
Isomers in which similar atoms or groups lie on the same side of double bond are ca lled the
Each o f carbon atoms 2 and 3 has the groups CH3, H, Cl and CHCICH 3 attached to it. The cis-isomers (Latin cis = on same side), and the isomers in which the similar atoms or groups lie on the
order of pri orities of groups is: opposite sides of double bond are called trans-isomers (Latin trans = across).
Cl, CHCICH 3• CHJ' H Such isomers which have the same molec ular formula, same structural formula but differ in the
Confi guration at 2C can be known as fo ll ows: relative spatial arrangement of atoms or groups about the double bond are called geometrical isomers
and the phenomenon is known as geometrical isomerism or cis trans isomerism.
CH H Maleic acid and furnari c acid are important examples o f unsaturated dicarboxy lic acids, which
I i I .
H--3c- CI Cl--3c- CH 3 exhibit geometrical isomerism . Tbese two isomers are shown below :
I
CHCIC H3
fAner1 wo
ln tcrch<mges)
, L t H-C-COO H H-C-C....:...COOH
~ C ICH 3
=S
II II
Configurat io11 H-C-COOH HOOC-C- H
cis-fonn rra ns- fo rm
Maleic acid (m.p. = IJ0°C) Fumaric acid (m.p. = 302°C)
 Both these isomers di fTer not only in physical but also in chemical propcrt1t:s .f- or cxampk,
maleic acid readily fonns an anhydride but fwnaric acid doe~ not. ~1alt:1c acid may bt: converted inlo
fumaric acid, when its aqueous solution is heated wi th a small amount of hydroch lone. acid. FLHnttril
acid may be converted into maleic acid by irradiation \V llh ultrav1okt lrght. fhc grl:Jtt:r c:n~t: o f anh) Jritk
formation indicates that malei~ acid is the u s-i';omer. Anh) dnck forn1Jtiun 1.., not ro~~,tik in lumttnc
acid (lran.s--i somer) as the two carboxylic group~ an: too for Jp~n . ·r he m1..·lt1ng po111t of m,1k1~ ,lL' HI i,
130°C while fumaric acid melts at 30::! JC. -rn~ dipole mnrnc:nt nr m.ikiL .11:1d j._ quill: high \\lllk th.it ol
fumaric acid is zero.
Geometrical isomerism is common!~ found in cth) lcrn: J1..-r1v ,1tiH: 1n \1,h 11.-h l'. itch (lt th1: d,n1hly
bonded carbon atom is linked \\ 1th t",Hl J 1tkr~111 grlmr-- '-tnmt: mu1L· l·,,1mrk-. .in.: L! i\t.:11 bt:IP\\
I. CH 3-C- II t II C H
II 1'
Cll 3-C If II C < II
(c n-1(omcr1 1 1r Jll I I ,rrn I
2-Butcnc (b p 4 l 1 f:u:..:nc lh r I I J
2. H- C Cl fl C' <I
I I
j
H-C CI CI C H
l< t.S - J!,(J01c! I (/rur, ~ i-., ,rnn I
D1t:"hlorLltlhene (b p "- t,U l U 1Lh!urocthc11c !b p I 'I ( J
....
-' . C H - C- COOH
6 5
C/L ( ( '()(J J-1
11 II
H-C- COOH HOO{, C H
(cis-b.omer) ( 1rwn-1wn1cr l
.·\ll ocinnJmic acid (b.p. 68-C) Cutnamu.: ac,d(bp 133 C)
CH.- C- H CH -C- H
-L _, II J II
HOOC-C- H H-C-CO OH
(cis-isomer) ( tr£lns- 1somcr)
lso-cro10011: nc,d (b.p. = l 68-l 69°C) Croloruc acid (b .p. = l 8Y' C)
 ~ ■ I-\ I l.:.,\ ll~Ll'\.,1 1'
1

\ )f '- "V " ~ .... ... . . _

In 1he di.u0 cl,111 ,,,unds, 1hc 1,1o g.r,.1up, :11 tnd1~d to c;ich nitrogen atom nr.: on th e sa1nc side a11 ct grou p of hi gher pri ority on each of th e ca rbons that are doubl y bond ed (C l and I) are on the same
side of the double bond and therefore the struc ture gets th e Z config uration_Based on the above

-
in lhc u111i-isomn. th,')' JI'\,' ,,11 lll' POSitc sides: '
argum ents, th e slruc ture
/ C0 1I~
H,L\
"~= t'!
-
C.H,
'
/
N= N H, 1 2/ 1
C=C
<'l ,1- l)1rhrll\ l l llftll'llium
11,Cl
o,1r1- l1 1ph~n yl J 1o?(m1um Cl/ " Br
above wi ll get E con fi gurali on since Cl and I on the tw o doubly bonded carbons are on the
J J,<l. 11 .4 E a nd Z Sys tem o f No me nc la ture
\\ 'c kno" 1ha11hc ~co111e1ri cal i,c>111cris111 is possib le in , 1ructurcs of the fo ll ow ing three types:
opposi te side to eac h othe r.
Simil arl y the confi gurat ional symbols to the fo ll ow ing structures may be ass igned as shown
a, ,J a, ,a be low eac h.
Type I: C= C :rnd C= C
b/ " b b, ' b
H, / Cl H"> / H
C=C
"
r rn 11J
C= C
Tvpr 11 :
J'
C= C
/ J a,
C= C
/ x H3C/ " H
HOOC/
z
COOH
and E
-
b
/ ', X b' 'a E and Z system is parti cu larly usefu l fo r assigning th e configuratio ns to a pair of ox im es. For
llt lll'i
example,
J ,
'c= c·
/ 'i. a, C = C/ Y
T"pe Ill:
. b' 'v and
b/ ' X
H3C,
/
C= N
..
/ OH H3C
" ..
C= N
cu trans H H/ ' oH
Z-Accta ldoximc" £ -Acc taldoxime
In 1he firsl rwo types in which ai least one group is common both to doubl y bonded carbon atoms,
tl1e !.'.eOmetricaJ isomers are !Jbe\led as cis and rra11s de pending upon whether the co mmon groups are lf the organi c compoun d conta ins two or more doubl e bonds capable of showing geometrical
on ; ame or oppos ite si de of rhe double bond. Ne ither th e cis-trans nor the syn- anti system of c, >
isomerism, E and Z notations are given to eac h double bond_ For exam ple.
configurational nomenclature is appl icabl e to the structures of type UI , where all the four substituents
are differcnL Moreover, these svstems of nomenclature are ofte n ambi guous bec ause the confi guration
descripri ons have not been de fined accordi ng to any genera l and cl ear set of rules. So an unambi guous H 3~"> / H H, / H
sy, lt'm of configura1ional nomencl ature for all types of struc ture show ing geometric al isomeri sm was
/
C=C
' -' , /
CH
6 J
HJ,C, • s,
/ C=C
de Yd opcd in 1968_ The system is kn own as EZ l)'Sle111 of110111e11cla111re and is based on the sequenc e
rulc-s of Cahn, Ingo ld and Pre log for naming opti cal isome rs on the R- S system di scussed earlier. In
H
H
/•C = Cs,H H
/
C= C
2 J,H CH.
6 '
order to specify the E or Z configuration ro as geo metrica l isomer. the fo ll owing rules are fo ll owed:
I For a doub le bond compoun d robe ass igned the confi gurati on, the two groups of each of the 2, 4-Hcxadie nc (2E, 4Z) l . 4- Hc:<adicne (2Z . 4Zl
do uble bonded ca rbons are arran ged accord ing to the priority sequence rules as in R and S rul es
fo r specifying confi gu rati on.
10.11.S Geometrical Isomerism in Alicyclic Compounds
, That isomer in wh ich th e two grou ps of hi gher priori ty (one eac h fro m the two doubl y bo nded We have observed that geometri cal isomeri sm arises only when tl1ere is hindered rotalion about
o rlmn) are on the same side of the double bond is ass igned tl1e confi gurati on. stand s fo r th e z z a bond . Such hindrance is not confined to double bonds only. For instance disubstiruted derivatives of
Genna n word Z11 , amm<"n meanin,; ' together'. If. on the other hand , the two groups of hi gher
cyclopropane, cy lcobutane, cyclopentane and cyc lohexane can also show cis-trans isome ri sm because
r non ly are on opposi rc sides of doub le bond, ihe isomer is given th e E confi gura ti on. E stand s
fo r the German word EmKef!.l!n , meaning, ' aga inst' . they fulfill the basic condition of hindrance to rotation about a linkage between atoms as joined in a ring
are not free to rotate around a sigma bond.
Cl, 1 2/ 1
TI1u s in , 1ruc1urc,
C = C, the two groups on ca rbon I are CJand H, out of whic h Cl has
H/ ' l3r
hi gher priu rity. Sim il arly out of th e group I an d Br on the ca rbon 2, I has pri orit y ove r Br. The
 - For example. 1.2-dimethyl cydohcx ane ,'xis1s in two gc:0111c1rical iso111cric fo nn s. If two methyl
IIIIIIIIMII •·~
I . Eclipsed conformation: In this conformation, the tetrahedrally anached three hydrogen atoms
:_';
~roups are on opposite sides of the ring, 1hcy art' trans and when they arc on Lh c sa me side they are ci.i·
lo front carbon are exactl y in front of those anached to the back carbon. i.e., hydrogen atoms
rh csc compounds are geometrica l isomt·rs of eac h other. ·
of both the ca rbon atoms are crowded together.
~ 2. Staggered conformation: In this conformation, the tetrahedrally anached hydrogen atoms
0 CH,
~ ,s-1 .2-Dinh.' Lh)

CH,
le! ck1h,.·,:m1.·.

H
H
/ CH,
r,,111.,- l.2-0 11111.:thylc ycloh~x rmc

to two ca rbon atoms are as far apart as possible. It is important to note the basic strncture of
th e molec ul e and the various bond lengths and bond angles remain the same in both the
conformati ons. These are ca lled Sawhorse method of representing the conformations.
(Fig. I0.9)
The following are other exa mples of gcomc1rical i,,,mcrs of cyc lic co111pounds. H H
Cpl·!, ,
H

I/
I

CH.
H

. V~", 0
CH, H 0 1-1 OH
<£)H OH r7c'"
I
H H
/C'H
I
1it-l .~-D1mcthyl
cyclopropinr
tnmi:-1 .: -D1methy I
C)cl,.,prnpJne
CIS-l .~-
CiclopcntJncd1ol
1rw1s- l ,:!-
Cyclopcnlnncdiol
/ c
'-----cL H
H ~ H I
H
CONFORMATION OF ALKANES Eclipsed Staggered
Rotati on arow1d carbon-carbon si ng.le bond. Single covalent bond (cr bond) present between two Fig . 10.9 Eclipsed and staggered conformations of Ethane
carbo n atoms is fo rmed by the overlap of thei r sp 1 hybrid orbitals along the inter-nuclear ax is. The
Newmon 's styk of representing the confo rmations of molecul es is more popular TI1us the
electron dislribution of the molecular orbital. thus fo nned. is cylindrically symmetrical around the axis
two conformations of ethane may be represented by Newman's projections as shown in
of th, bond. Due to tl1e axial Jymmctr\' of the mnleculor orhira/. rotation around !he C-C bond is
Fig. 10. 10 .
almost f ree. As a result of this rota ti on, alkanes can have different spatial arrangements, i.e. different
re lative arrangement of thei r atoms in space. " - H
H
~
Such different spatial arrangements of a/oms or gro ups of atoms in a 1110/ec11/e that can be
H
rr:adilv imcr-coni·erted by rota/ion am1111d C-C si11gle bond are called ca1tfor111ers. They are rotational H
isomers and th e phenomenon is caJled. confo nnational isomerism. The molec ular geometry corresponding
~
10 a co nfom1 er is known as conformat ion.
/10, 12.1 Conformation of Ethane
H H H H
In ethane molecule, if it is supposed Lhat the position of one of the ca rbon atoms is kept li xed and H
1he other is roLatcd about it, a large number of arrangements of the hydroge n of the ca rbon with respect Eclipsed Staggered
lo the hydrogen of the other ca n be obtained. Ou t of Lh c inlinitc number of poss ible conform ati ons of Fig. 10.10 Newmen's projection for the conformations of Ethane.
ethane. two confo rmati ons represent lhc ex tremes. as shown in Fig. I0 .9. These are :
,/) I. Eclipsed conform ati on In New man projection, the two carbons fanning a bond are represented by two ci.rcles, one
behind the other, so that only the front carbon is seen. The hydrogen atoms anach.:d to the
/ 2. Stai,;gercd ~onfonna lion.
front carbon are depicted by C- H bonds from the centre of the circle. The C- H bonds of
the back ca rbun are drawn from the circumference of the circle.
One confomrnlion of ethane gets converted into the other when rotated through an angle
or 60°.
 -
Relative Stabiliti es of Conformations of Ethane
It must be pointed out here that HH
10.12.3 Conform ations of n-Butan e
:>TER£0CHEM 15TRY ■ lliila
"~ :
rotation around the sin gle bond is 1101 H H H H
completely free. (fit were-so, the potentiJI I 1 I, I3 I4
energy of different conformations should H H-C -C-C -C - H
have been the same. But in acn1al practice, I I I I
H H H H
the potential energy of the molecule
changes somewhJt with the rotation around
C-C single bond. Thus the potential
r If we consider the rotation around the single bond between two carbon atoms
11-butane, we see that molecule is similar to ethane except that one hydrogen on each
(C2 and C) of
carbon has been
energy of ethane molecule is minimum for I 2.6 I kcal replaced by a methyl group
staggered conformation and maximum for ~ per mole
'-'
eclipsed confonnation. The difference "
LJ.J
H H
between the two being 12.6 kJ moJ- 1. In ~
I, I.
(i.e., CH -e·- c '-CH)
/:«
otJ1er words, s1aggered co11forma1io11 is rhe i: 3 3
'-'
0
I I
::&'H~
most slable conformalion of elhane while c.. H H
eclipsed co11for111alio11 is 1he leas/ s1able The various possible conformations of n-butane are:
(Fig. 10.11 ).
(1) Anti conforma tion (l): In this conformation. methyl groups and hydrogen linked to two
The small energy difference H H carbon atoms (C and C) are at a maximum distance apart. It is assumed that the
between different conformations is due to Staggered 2 angle of
rotation around the C - C bond is zero for this conformation.
the repulsive interactions between the 2 3
Fig. 10.11 Relative stabilities of conformations of Ethane (ii) Eclipsed conforma tion: Starting from the anti conformation, ifwe rotate
electron clouds of the C-H bonds attached the C2 -C 3 single
to the central C-C bond. In the staggered confonnation of ethane, the electron clouds bond through 60°. we get the partial.ly eclipsed form II. In this confonnation,
of these carbon the methyl
group attached to one carbon atom is at the back of hydrogen atom (rather than
hydrogen bonds are as far apart as possible. But in the eclipsed conformat ion, the tJiree the methyl
C-H bonds of group) attached to the other carbon atoms.
one carbon are closest to the three C- H bonds of the other carbon. The repulsive interaction
s between (iii) Gauche or skew configura tion: On rotating C - CJ single bond
the electron clouds in this position increase the energy of the molecule and thus decrease 1 by another 60°. we
its stability. get the staggered conformat
But the energy difference is not large enough to prevent rotation. Even at ordinary temperatu ion. Ill is also known as gauche or skew form. In this conformat ion,
re, the various bonds are farthest apart but the methyl groups make an angle of 60° with
the molecules possess sufficient thermal or kinetic energy to overcome the energy barrier respect
through effective to each other.
collisions and thus confom1ations keep on changing from one fom1 to the other. As such
it is not possible (iv) Fully eclipsed conforma tion: Rotating the C - C bond by another 60° gives rise to fully
to separate the different conformations of ethane.
eclipsed conformation (IV). In this conformation. 3the methyl groups and hydrogen
1
atoms
10.12,2 Conform ations of Propane ~ attached to two carbon atoms completel y eclipse each other.
In case of propane (CH3-CH 2- CH ) rotation can take place about either Further rotation of 60° gives rise to the gauche form (V) in which the methyl groups
3 of the two are again
carbon-carbon bonds. The energy difference between the two extreme conformations 60° apart. On further rotating C - CJ bond by 60°. we get another eclipsed conforma
1 i. e. eclipsed and 2 tion (VI). Still
staggered, is 13.8 kJ mo1- which is nearly the same as in case of ethane. The most stable further rotation of C - CJ by 60° and thus completing the rotation through 360°.
confomiat ion 2 we get anti fonn (I)
is the staggered conformation although it can freely change into the eclipsed conformat again.
versa. ion and vice
The various confomiations are shown in Figure I0. 13.
H
CH 3 H
CHi CH3
H CH3 H H H
H3C
H
H
H H H
H
H H
CH3
H
H
,CAHH H H
H
H
Fig. 10.12 Newman's projections for the conformations or propane. I II Ill
(Fig. contd ... )
 I A TE..xruOOK OF
~
■
~
ENGtNfE>{JN'-• '- r-" _,.,..., :)TI:.Rtl)(_Ht..MI~ I KY
CH,
CH,
CH, I CH) I 1-1
JH,
di HAt,
H3CH
HAH
1-1: f Hl-~ 1-1

1-1
H/ \ ' 1-1
H,C
;&HH

H H
Fully Eclipsed
H H
H Cl-1 1
H H Eclipsed
Eclipsed
\I
VI
IV
Fig. 10.13 Newman's projection for the conformations of n-butane
i
~ (4.6 14.6
Relative Stabilities of Conformations of n-Butane 'J
The stability of confom1ations of n-butane is in the order: "
Ll.J
KJ/mol
]
Fully eclipsed < partially eclipsed < Gauche < anti c
---- - -- _y ____ - - -- \.
(IV) (II and Vl) (III and V) (I) CH CH
(i) In fully eclipsed conformation IV, there is maximum repulsion between the bonding electrons t lttyt':;-HH,C_x!x_H H~ CH
3
H~H
and bulky methyl group. Repulsion between bonding electrons produces torsional strain in
the conformation while the crowding together of the bu!J...-y methyl group causes steric or H~ H H H H H CH H H CH H
J J
J
lander Wall s srrain in the molecule. Due to torsional strain and steric strain, this confom1ation Anti
Anti Gauche Gauche
has maximum energy and minimum stability.
60° 120° 180° 240° 300° 360°
(ii) In the partially eclipsed confom1ation (Li and VI) the repulsive interaction between the bulky
methyl group and bonding electrons is less than in fully eclipsed conformation (IV). Thus. Ro1a1ion -
partially eclipsed co11for111atio11s ore more stable than full_v eclipsed co11for111ation. Fig. 10.14 Energy Changes during rotation around the carbon-carbon bond In n-Buiane
(iii ) In gauche conformation ( Ill and V) there are weak repulsive interactions between two methyl
groups as they .ire 60° apart. ln other words, there is a slight Van der Wall's strain but no
torsional strain. Thus, it is more srable rhan partially eclipsed conformation. ISOMERISM IN TRANSITIONAL METAL COMPOUNDS
(iv) In anti conformation (I). the repulsive Interaction between the two methyl groups and bonding
electrons is minimum because the two methyl groups are maximum distance apart. Thus, this Transition Elements
conformation is free of lorsional as well as steric strain. Hence it is the most stable The transition elements are those which either in their elemental state or in their commonly
conformation. occurring oxidation states have partly filled d- and f-sub-shell. d-block elements usually are called
Iv) As anti conformation and Gauche conformations have staggered arrangements, they have transition elements andfblock elements are called inner transition elements.
maximum energy and maximum stability (anti conformation is slightly more stable than
The transition elements are the elements which show a slow and gradual change in characteristic
Gauche conformation). These conformations are referred to as conformational isomers.
similarity between highly reactive s-block elements on one side and p-block elements on the other side
(1·0 The difference in energy contents between conformations I and IV is about I8.4 kJ mo1- 1,
of the periodic table. It is also from their position in the periodic table where they lie between the most
between I and 11 (or VI) is about 14.6. kJ mol- 1 and between I and Ill or V is only
J.8 kJ mot- 1. electropositive s- and the most electronegative p- block elements and thus represent a transition (change)
from them and are called transition elements. They are also called d- block elements because the
(vi,) Maximum energy difference between two confomiations is only 18.4 kJ/mol which is easily
successive electrons are added in the d-orbital of the (11 - I) or penultimate shell. Their last two shells
provided by colliding molecules at room temperature. Thus various confomiations of 11-butane
are inter-convertible and hence cannot be isolated. In other words rotation around nre incomplete. They lie in the groups 3 to 12 in the periodic table.
ca_rbon-carbon single bond inn-butane is almost free. At any time, 11-Butane at an equilibrium Thus. the d-block elemems ore defined as the elements in which last electron enters in d-sub
will be_mixture of_all the possible confonnations which contains the highest percentage of shell of their pe1111lrimote shell (n - I ) i.e.. next to the outermost shell.
th e ant, conformation(s) and least proportion of the fully eclipsed confonnation (IV).
llill:a ■ l l.Xll!LY\..11'\\.'l'" "'"'"""' ' -- ■ ....
~
M !>TEREO<-Ht.h1I~IKT
ElectrOni( Confi5?uration of Transition Elements ~~;
The d- block clcmcnLs m· cla, sified :is tr:msition scri('S or clement with incomplete Jd, 4d, Sd A complex molecule consists of a highly charged positive metal ion (Lewis acid) with vacant
or ti-orbital capable of receiving lone pairs of electrons from ligands artached to the central metal ion or
and &d N1'itJI. lli,·) JI\' mad,· up \lf three ,oniplclc "'" s IO ckmcnts each and nn incomplete founh
row in the 1,,11!! fonn ,,r p,:riodic iabk. ·
c~u rion. Although the -ls• orbirnl pt·netmtes chiscr to the nuckus than 3d orbitals and therefore
atom to fonn a complex ion is called co-ordination number of the centrnl metal atom or ion.
The stability of the complexes increases with increase in atomic number of the dement. Moreover,
the complexes of atoms with higher oxidation stares and thus smaller size are relatively more stable.
[
lrns Im, er energy. the com cntion for writing tlw electron notations or transition clements is to writ~
Complexes have linear. square planar, tetrahedral, octahedral, square pyramidal or trigonal ;..i
cl,•,trons in (11 - I )J .md n.-.1rbi1als. There arc two reasons for this:
bipyramidal structures depending upon the type of hydridization involved during their formation .
(a) h•niwtion of tr,msition metals ,s due to loss of 11s-elcctrons (of course with exception). ;::
(/ll Th_c prohabi lity plot ,,fns ckctnins shows that these electrons have a greater probability of Lewis ucids Lewis bases Complexes Co-ordination I Type of Structure
bcmg far frnm the nucleus. while the (11 - I )d clectr00 are rdat,vcly buned deep inside the (ncccptors) Number I hybridization
atom. (Ccntnl metal ions) Ligands (donors)
This make the s-orbitol JS the l'>oundal') orbi tal in a neutral atom. [Ag(N H3l:r 2 sp
Ag• + 2NHJ ➔
Table IO. I. Outer rkctronic configuration of transition metals, cu•: 4 NH3 [Cu(NHil.f · 4 dsp"
A
+ ➔
[Zn(CNJ,J-2 4 sp3 I l
Zn2-t + KN ➔
=,m TrJns11wn 1,d\ series (Sc- Znl 6 cfsp3
+ 61-ip ➔ [Cr(Hp.Jl-
21 'C 1-:Ti :.,v :,Cr :,Mn :/e :1CO : 8Ni lOCu* ioZn
!Ar] 3.1' ~,.: 3,F 4;.l 3d3 -h~ 3cf 4,.: 3d' 4s1 3'/' 4s1 3d1 4s2 3Ji 4s1 JcflO 4sl 3c1104.<1 ·ism in T ransition Metal Complexes
Co-ordination compounds and complexes have same chemical formulae but different structural
Second Tr:ms111011 (4dl s<ncs (Y-Cdl
arrangements. Such compounds are called isomers which have different physical and chemical propenies.
,,Y I
, 1Nb• ,:Mo• .i;Tc• .uRu' 45Rh' ,_Pd" ,1Ag' 48 Cd There are two main types of isomerism
1Ar]4d15~ I :;,,,-2 I
4d' ss 1 4.t s,1 4a" 5s' 4d1 5s1 4a'8 5s 1 4(/10 sso 4(/IO 5s 1 4d10 5s1 (A) Structural isomerism (B) Space or stereo isomerism
Third Tr:insi1ion (5d) scri<s (Ln- Hg) (A) Stru ctural Isom erism
~7La 7, Hf nTa ,.w ,,Re ,.os These isomers have same molecular fonnulae but different stmcrural arrangements of atom around
71 lr 1sPt ioAu soHg
\Xe]5d16s1 5d' 6," set 6s2 central metal ion.
Sd' 6--1 5d' 6i 5,1> 6/ 5d1 6s1 5d' 6s 1 5d10 6s 1 5c110 6s:
It is mainly of the following types:
Fourth Transition (6d) smes (Ac-1'11.) I. Ionisation isomerism: Ionisation isomers yield different ions in solution although they have
,.,Ac ,.,Rf IVlDb I '""Sq 107 8h 1osHs IOYMt 110D5 IIIRg lllCn
same composition. This type of isomerism is due to the exchange of anions between the complex
1RnJ6J' 7,: 6a- 7s' 6d3 7:s' 6d' 1s' ion and the ion~ outside it, i.e.. in coordination sphere. For example, [Co(NH,J;Br)SO, is red-
6cf 1s' 6a" 7s2 6d1 7s: 6c/' 7s1 6d10 7s 1 6d10 7s2 violet and in solution gives a precipitate with BaC1 1 confirming the presence of SO]- ion.
10.13.1 Complex Formation by Transition Elements On the o~her hand, [Co(NH3 ) 5SO,)Br is red, and does not give test for sulphate ion in the solution,
but instead gives a precipitate of AgBr wi ll AgN03 .
Transition metals fonn a la rge number of complex compounds. Here the metal ions bind a number
of anions or neutral molecules (cal led li gands) giving compounds showing characteristic propel1ies. Other examples of ionization isomerism an::
Some example of such complex compounds are: (i) [Pt(NH 3),(0H)1]SO, and [Pt(NH 3),SOJ(OH)1
[Fe(CN)0jl- , [Fe(CNJy- [Cu(NH;Jl +. IP!Cl,J2- (ii) [Pr(NHi)P 2]Br2 and [Pt(NH 3),Br1]Cl1
Their tendency to fonn complexes is due to the following reasons: (iii) [Co(NHJ) 5 N03]SO, and [Co\NH i)5 SO,JNO,
ti) The presence ofvacem Cn - I )d orbitals which can accept one or more electron pairs from 2. Hydrate isomerism: Since water is one of th.: most effective co-ordinating agems, therefore.
ligands.
the number of water molecules which may enter imo the co-ordination sphere may vary resulting
(iiJ High charge density due to small size and high charg~ of the transition metal ion,
(iii) Ava ilability of ~everal o,:idation states.
in the fonnation of hydrate isomers. For example, there are three different hexa-hydrates of
chromic chloride with an empirical fomrnla ofCrCl 3 · 6 H20 . One of these hydrate is violet and
r.'
1111 1 A TEXTBOOK OF ENGINEERING LHEMI>. KT
the other two ar~ green in co lour. All the three differ in the number of molecules of water in th
co-ordination sphere. T he fo m1ulae which have been assigned to these hydra te isomers are : e
ICr( HplJC' I_, [Cr( Hpl, Cl] C I, · Hp [C r(H p) 4 C l2]Cl · 2 H 2 0

6.

.:, I tK.t:.U'-,JH:.r•IIJ I.-.. ,

Ligand Isomerism: This isomerism arises in those complexes in which the two ligands are
isomers themselves. e.g..
H,C--CH- CH 3

-
---
H, C- CH-Cf-1 3
Dark green .I I and .I I
Violet Bluish green NH 2 NH 2
NH 2 NH 2
(three ionic chlorines) (two ionic chlorines) (one ionic chlorine) I, 3-diamino pro pane
I . 2-diamino propane
Si mil arh' other compou nds in which hydrate isomerism is observed are: When these fonn the complexes, we get ligand isomers. This type of isomerism is quite rare.
(il [Co(NH 3 )iHPlCl)Cl 2 and [Co(NH 3) 4C l2)CI · Hp 7. Polymerisation isomerism: Thi s is not true isomerism because it occurs between compounds
(ii i [Co(NH J)/ Hp)C l]Br 2 and [Co(N H) 4Br2]CI · Hp hav ing the same empirical formula. but different molecular weights. Thu s [Pt(NH 3 ) 2 Cl 2] and
J . Linkage Isomerism: Isomerism of thi s type occurs when more 1hc111 a single a/0111 in a ligand [Pt(NH 3 ) 4 ][PtCl 4 J have the same empirical formula.
111ayfi111c1io11 as a donor. Such ligands are called a111 bide111a1e ligands. For example, in the case
ofN0 2 either a nitrogen or an oxygen atom may act as donor g iving two different isomers. Thus (B) Stereoisome rism or Space Isomerism
two different isomers with molecular fonnula [Co(N0 2)("NH 3)sJ"+ha ve been prepared. One isomer Thi s is due to th e different relative positions of the ligands. It is of two types :
has N -atom of NO, group linked to cobalt atom and the other has 0-atom linked to cobalt I . Geometrical isomeri sm 2. Optical isomerism
,. 2'
I. Geometrical isomerism: Geometrical isomers differ in the spatial distribution of atoms or
groups around central atom or atoms in polynuclear compounds. Those complexes in which
l
NH. . NH ,
j
H3N "-. ; , ONO the two same li gands occupy adjacent positions to each other are called c is-isomer while
H 3N "-.1j,,,--N0 2
ligands occupy ing position opposite to each other are called /rans isomer.
HJN / j
Co....___,
NH3
N Hi
1 r
H3N/
NH 3
]
I .........._N H3 This isomerism cannol be exhibiled by co-ordinal ion compounds having 2 or 3 co-ordinal ion
number as ii is no / possible 10 have more than a single arrangemenl of ligands in space
around !he Ce111ral-io11 in lhese cases. Geometrical isomerism wilh respec/ to !he m e/al has
Ni trilo-pcnt:unmrnecobalt (I ll) ion (Red) N11ro-pca1ammineeoba lt (Ill) io n (Ye llow)
also no/ been fo und among lelrahedral complexes offype MA. or MA , B, (where A and B
Other Examples are: represents li gand s) which do not s how this isomerism because all the · four ligands are
U) [Cr(H , OJ , SCNf· and [Cr(H 20) 5NCSf• equidi s tant from each other. Thi s type o f isomerism is shown by square planar and octahedral
complexes.
(ii) [(NH 3j/~y)2Co(N0 2), ]N0 3 and [(N H 3 JiPY) 2 Co(ON0) 2] N0 3 etc.
(a) Cis-trans isomerism in square planar complexes is of various types:
"· Co-ordination Isomerism: Thi s type of isomeri sm is possible when both positive and negative
(i) Any complex of the type MA 2 8 2 can exist in cis-/rans form.
ions ofa sa lt are complex ions. The two isomers differ in the distribution of ligands in the cation
(positive ion) and the anion . A A B A
Two important examples are: ' M
/ ' M
/
(i) [Co(N H,J 6] [Cr(CNJ6 ] and [Cr(NH 3 i6 ] [Co(CNJJ B/ "s A/ "s
cis- trans -
(ii) [Cr(NH 3 1 J [Co(CP.h l and [Co(NH 3 )6] [Cr( CPih l
(iii) [Pt(NH 1 ).J [PtCl 6 J and [PtCl 2(N H 3 ). ] [PtC1 4 ] It is because the ligands may be equidistant from the central atom, but they are not
equidistant from each other. Consequently it is possible to distinguish between li g ands
This type of isomerism may be caused by interchan ge of ligand between the two complex ions.
that lie next to each other on the edge of the square and those which lie opposite to each
S. Co-ordination position isomerism: Thi s type of isomerism is due to 1/,e di.ffere11ce in !he other on the square diagonally.
distrib111ion of ligands i11 lwo coordinalio11 cenlres. Generally !he bridged complexes i11 volvi11g
differen/ ligands .\'how th is isomerism e.g .. Thus geometrical isomerism is an important key in co-ordination compound with co-
ordination number 4 and 6. The cis-lrans pos itions in square planes and octahedral
complexes are reviewed as follows :
l
2,
2+
l
__... OH . .___ 5
Co(NH 3 J,C I, __... OH . .___
(H 3N ),Co
' oH ---- C( H3 NJ 3Co Co(N H hCI ~ I ~ I
J
3
[ ' 01-1 ----
Un !-+ymmctri ca l
Symmct n ca l 3~
3~
(a)
6
Square planar
Octahedral
~ ■ I\ I E..X IUOUK Ut C NV INt.t.Klf'iU '-'''-'"" -''' •·
The positions 1- 2. 2- 3, 3-4 and -1- 1 in the square planar complexes arc
cis w.r.l. each
- complexes of the type,

.:JI t.KJ:V\..nCJV IIJ I " ' • ~

al complex ( vi) Geometrical isomerism is also shown by bridged binuclear planar
other whik· p0sition 1- 3 and 2-4 are 1r<111s to each other. Similarly in octahedr
2- 6, 6-J , etc., M2A2X4, e.g.. [PtCllE t3Ji.
1- :S. 2-4 and 5- 6 positions are 1ra11s to each other whereas 1- 5, 2- 5. 1- 2,
posi tions are ris to eac h other. Cl . ._____ _,,,....Cl -----.._ _,,,.... Cl PEt3 .,...Cl .,... Cl
pl atinum or '--- Pt .....- '--- Pt .,...
Fo r cxum pk. the squ are planar c0111plex of the type MA 2B2 i.e., cis- Pt Pt
' EtiP Cl .,,,.... '---c1 .,,,.... '--- Etl
PEt3/ '--..Cl /
dichloro-diammin e plati num (II ). [Pt(NH3):C12] can exist as under:
CIS - trans-
/ Nl-1 3 most important
Cl'-.___ / Cl Cl lb) In octahedral complexes, several kinds of cis-trans isomers are known the
HJN /
I Pt
'-.___ NH,
I I) r1"' I
--'CI
one being cis-truns isomers in MA 4 B2 and the cis and trans isomers in MA 3
B;·
tetramminecobalt
HJN- (i) Example of the MA4 B2 type octahedral complex is furni shed by dichloro-
cis- trnm:- (Ill) complex ion, [Co(N H3 ) 4 Cl2]'. It shows cis-trans isomerism
as given below :
(ii) Co mplexes of the type [M(AA) 2]. MA~. MA 3B and MAB 3 do
not show this isomerism
since ull possible spatial arrangements for any or these complexes are identical. ]+ ]+
I
N"-.,ICl /
I
(iii) In a complex of th e type MA:BC . also there are cis- and
trans-iso mers, e.g .. H2 Cl
Cl
I
H3N"- _.,,,....,,,-N H3
[Pt(NH_J FIN0 2] can exist as: f_,_,,,....,co"- / /_.,,,....,,,-co"- /
n· R3N I NH) H3N I NH3
NH3 Cl
O,N"' / Cl 0 2N"' / NH 3
H3N /
I Pt
"'-. NH
I I
_,,,,,.-- Pt " ' I cis Viole! trans G reen
by [Co(NH 3) 3CIJ It
3 H3N - - C I (ii) Example of the MA 3B 3 type octahedral complex is furnished
cis- trans- shows the following two geometrical isomers.
displays possible
(iv) For a complex of the type of J\1ABCD, where all ligands are different Cl Cl
isomers. e.g.. [Pt(py)(N H3)BrCI] can exist as:
Cl I _.,,,....,,,- NH, H3N" I _,,,/' NH3
H3N" ' / Py H 3N " ' / Py / Br
/ " co / · /_., ,. . , ,- co"- /
H3N" ' H3N " ' / Cl
\.,,,,,..rt" - \ I I I Cl/ I" NH3 H;N I NH3
CI - - - B r
_,,,,,.-- Pt ""
Br-- -CI
I
_,,,,,.-- Pt " -
I
_,,,,,.-- Pt " - ' Cl Cl
Cl--Py Br---Py
[I · cis-or foe (focial) 1rnns-or mer (Meriodina l)
IV Ill
, where AA can be
These three isomers are written by fixing the position of anyone ligand (say
NH ) and (iii) Even M(AA) 2B2 type of complexes also show cis and /rans isomerism
anionic ligand
positions of other three li gands (py, Cl and Br) trans to it. In structures III and
JV in 3which any symmetrical bidentate like ethylenediamine (en) and B can be any
Br is trans to Cl are identi cal structure. such as c1-, CN-, N0 2etc.
s if the chelate
(11) The geometrical isomerism can also occur in square planar complexe
1®1.l l<~Pl
s between
group is not symmetrical, i.e.. un symmetri cal bidentate ligands, e.g., complexe
glyc ine (NHF H2COOH) and platinum i e , [Pt(gly)2] .
H,C-H N------ -N H,- CH, H C - H N-······ NH-c o
-1
:/ "-. :
l :"
: Pt
/ : -
: I- ll l:"- /:• l
· Pt
I
oc --o - - o -- co OC-- O - - NH 2-CH 2
:/ "-. : cis- trans-
cis-
trans-
Another example of this type is [Pt(en):C lq]
l Note:
(1) [MA 5B] does not show geometric al isomerism .
(ii) [M(AA) 3]3 · docs not show geometric al isom~rism .
-
- (il')Complexes having six different_ ligand~ [M(ABCDEF)] s h e ~
:ti!:. ... ...:a
. •.
1somens1n. Tlieoreticall)'
'
fifteen different isomers should be possible I geoinetric 1
• n pract · a
isomt·rs of th<' complex [Pt(C, H,N)(NH,)(N02)(Cl)(Br)(l)] have actually bee/e, three STEREOCHEMISTIIY I ..
·cal isomerism· Optical isomerism arises when a compound can be-rep
2. Opt, . . . . resentedisolated
b . 3-
asl'llunetrical structures (!mown as opucal isomers). The two isomers are structu II y lwo 3-
- ofeach other Uust · as m · the organic · chem1stry
. ). Further 11· has been
ima<•e found thra IYthe rn1rror
·
" · I I I d at hese ,
imo"e.s compoumls are non- supenmposab e 011 eac I ot 1er an they do not po•,,sess. the n1rror
symmetry. The optical isomers are called dexrro and laevo (d and/) depending upo h ~1ane of
in which plane of the polarised light is rotated. Then d and I isomers of a comp n Ide direction
. .
enantiomers or enanllomorphs. The phys10/og,caI b h .
e av1our of the enantiomers oun are I
is . ca led
· tobacco 1·s q111te
. toxic
. Ihan d-111cot111e
· · prepared in
e g.. /-11ico1111e preselll m the I bquuedi"-
'JJere111
a oratory.
Mirror
10.13.3 Optical Activity in Octahedral Complexes
(c) Examples of M (AA) B X type: Compounds of the formula [M(AA)B .l½] containing one
Optical isomerism is common in octahedral complexes involving 2 or 3 symmetr· . 2 2 2
symmetrical bidentate ligand also show optical activity, e.g.. (CoCli(NH )z(en)t ,
groups (i.e. a group attached to the central atom by two co-ordinate bonds) of the type: ica1bidentate 3
[PtC1 2Brz(en)].
[M(AA)2X2] and [M(AA)3] where AA = bibentate ligand.
This is illustrated as under:
Cl Cl 3+
(a) Example of M(AA),X, type: The complex ion is cis-dichloro bis /ethylen d' .
(III)
.
ion.
• +.
[Coten)aCI,]
,, e wn1111e) b I1
- . The above two are opticalforms. There is also a,11·11ac11ve
due to tI,e presence ofa plane of symmetry a11d is shown below:
. co
transfi a ~----~c, Cits:.: I 71 -.....
orn,
en-N 1+ + +
( N-en Cl NHi Cl
!'W[
N--t-
i-C
/I
Mirror
/)c\/ 10.13.4 Optical Activity in Tetrahedral Complexes
N
' en]
I Cl
c,/ j"-y The optical activity has been observed for chelated tetrahedral and square planar complexes but
only rarely.
N N- en
Cl In tetrahedral complexes only the type which occurs in bfc-chelates with unsymmetrical ligand
has been detected. These have been found in Be(Il), 8(111), Zn(II) an Cu(ll) complexes.
cis-mirror image
(optical aclive) trans They are of the general type as represented below:
Optically inactive fonn
Another example is [Pt(en)oCl
2
].
(b) Example ofM(AA)3 type: Examples of the three bidentate ligands in octahedral complexes
are [Cr(en);J3+, Iris (ethylene diamine)-chromium (Ill) ion and [Cr(C 0 )i-,
trioxalato-
AO BBO A
chromale (fll) ion.
3+

2 4
3+
A6 B86 A
Thus bis (salicylaldehyde) boron (Ill ) cation has been found to be racemic and resolution has
been accomplished.
[©(c> <o:©J].
0
8
CH
Mirror
ma • A l t.A I PVV••- ·
STEREOCHEMIS'TRY I lliilliia
The t,io ~n:uitiomas oi bis (bc11:o_rl-a,.:to11uto) bcrvllium (l l) are shown be low · ------
8. Pair of enantiomers ( I : I mixture/racemic mixtu re) rotates the plane of polarised light by equal
/lie Me amounts in opposite directi ons. Thus net rotation is zero.
111 \ / ~le '\. / 9. If plane of polari sed li ght is rotated towards ri ght, the compound is dex tro rotatory. (d) or (+)
C=O O=C
C=O O=C\ I \ I \ fo rm and if plane of polarised light is rotated towards left, it is called laevo rota tory, I or (-) fom1 .
I \ I HC\ Be CH
HC. Be CH \ I \ II I 0. Since two enanti omers have identical properties thus they cannot be separated by common physical
\\ I \ I/ C- 0 0-C
C-0 C- 0 I '\. techniques.
I '\
Ph Ph Ph Ph 11. Diastereomers have different spatia l arrangement s of atoms with different phys ical properties.
12. Molecule with ·11' chira l centres will have 2" stereoisomers which may or may not be optically
~tirror active.
that 4 di fferent •croups around the. central atom are not required 11r0 r . 13. Meso compounds ha ve a plane of symmetry, thus they are optically inac tive.
It ma). b·< not~d- " . • optical
Jcti i ity. All that is required is that the molecule should be dLIS)'t11111etr1c so that II can exist in two Fonns 14. When equal quanti ti es ofrwo enantiomers (dextro and laevo) are mi xed together, it results in th e
ll'hich are mirror images of each other, as sho1111 above . formation of optically inactive racemic mi xture.
15. Compensati on of optical rotati on/ac ti vity due to one half of a molec ule by another half of same
Jr may also be noted 1h01chelare groups are 110 1 required. as a principle for optical activif\:
molecule is called internal com pensation which exist in meso compound.
Ho,..ei·<'r. most of1he kno,rn examples invol,·e chela1e groups. Thi s 1s probably due to greater sta bili~
of such compb:es 11hich makes their resolution possible. 16. Exact cancellati on of rotation of one molecule (dextro/laevo) by another molecule (laevo/dex tro)
is called external com pensa ti on wh ich exists in racemic mixture.
As can be sw1. it has no plane or axis of symme try.
17. Assignin g of configuration by relating thei r confi guration with other molecules is known as
Square planar complexes are seldom optically acti1·e. One such compound which has been relative configura tion. e g. , D and L.
resolved into two fonns is shmrn belo11:
18. Assigning of the exact or acn1al confi gurati on to a molecule is known as absolute configuration,
2.. :. e.g., d and /.
H H 19. Geometrical isomeri sm ex ists in compo und s cont aining ca rb on-carbon doubl e bond in whi ch
'\_ H 2 H2 /
C- -N N- -C. _ molecules assume ri gid configuration due 10 hindered rotat ion.
Pb -- I \ / I -H 20. When similar atoms or gro ups lies on same side of dou ble bond. it is ca ll ed cis-isomcrs :md
\PtI when they lie opposite side, it is call ed trans-i somers.
2 1. Similarly if higher priori ty groups lie on same side of doubl e bond then molec ul e as is designa ted
M\I / \ J/ Me ·z- (Zusammen). If higher priori ty groups lie on opposite side of doub le bond then molecule is
designated as ' E" (Entgegen).
,C -NH, NH,- - C,,
22. Rotation around C- C single bond give rise to various confo rmati on.
Ph
Mc 23 . Carbon-Carbon single bonded molecules exist in three different confo rmat ions-staggered. skew/
gauche and eclipsed.
As can be seen, it has no plane or axis of symm etry.
INFORMATION WINDOW
/ 24. Ind-block elements last electron enters in d-subshell of th eir penultimate shell (11 - I).
25. Transition metal lies between the most elec troposi ti ve ·s' and electronega ti ve ·p' block elements
and thus represents a change (transition) and called transition element.
26. Transition metal with anions or neutral molecules (ca lled ligands) forms large number of complex
I. Isomers are those compounds which have general molecular fonnu la but d1 ers . their structure.
'ffi 111 compounds.
2. S<ru,rura] ;somm aed ,tece,;som,o '""" ma;" classes of ;som, ops
27. Transit ion met al co mplexes sho w two types of iso merism- structure and space or
J. S<n,erural oome,; may ha,e ''"'"""'me<rn, •oo ,
nJPAC oames, sameo, d,.ffimo t functional gro
. . stereo isomerism.
d;ff,,, m physkal md eh,m;e,J pmpen;e, aod <hey beha,e d;ff<reoHy ;, , h,mkal "'"' .,u,d 28. Ionisation isornerism--<:omplexes giv in g different ions in solution but ha ving same composition.
4. Stereoisomers have same IUPAC names as they differ only in spatial arrangement (
29. Hydrate isomerism: This ari ses due to nw11ber of wate r molec ul es which enter the co-ordination
configuration) of atom s, but they contain prefixes li ke cis-trans and leavo or dextro. sphere of transition metal compl exes.
5. Three dimensional arrangement is ca ll ed con fi gu ration.
. of 30. Linkage isomerism: When more than one atom in a mono dentate ligand function as donor atom,
6. S<e'<o;some,s '""'' ;, sam, fuoe,;,,. I gm, ps
E then linkage isomerism ex ists.
7. plane ·
nannomers have
polarised I'dent1ca
light. · and physica l properties and they differ on ly · roiauon
· I chem1ca!
111