SPINEL & INVERSE SPINEL STRUCTURES

The spinels have the general formula AB2X4.

Where:
A
II
= a divalent cation like Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, n
!
III
= a trivalent cation like Al, "a, In, Ti, #, Cr, Mn, Fe, Fe, Co, Ni
$ = %, , e etc.
Structure of Norml Spinels !AB2"4#$ The divalent A
II
ion& occu'( the tetrahedral
void&, )herea& the trivalent !
III
ion& occu'( the octahedral void& in the clo&e 'acked
arrangement of o*ide ion&.
A normal &'inel can +e re're&ented a&: !A
II
#
tet
!B
III
#2
oct
"4
,.g. MgAl-%. /kno)n a& &'inel0, Mn1%., ZnFe-%., FeCr-%. /chromite0 etc.
Structures of In%erse spinels !B!AB#"4#$ The A
II
ion& occu'( the octahedral void&,
)herea& half of !
III
ion& occu'( the tetrahedral void&. It can +e re're&ented a&:
/!
III
0
tet
/A
II
!
III
0
oct
%.
,.g. Fe1%. /ferrite0, CoFe-%., NiFe-%. etc.
The a+ove inver&e &'inel& can al&o +e )ritten a&:
Fe1%. = Fe
III
/Fe
II
Fe
III
0%.
CoFe-%. = Fe
III
/Co
II
Fe
III
0%.
NiFe-%. = Fe
III
/Ni
II
Fe
III
0%.
The num+er of octahedral &ite& occu'ied ma( +e ordered or random. The random
occu'ation lead& to defected &'inel&.
,.g. NiAl-%. for )hich the formula can +e )ritten a& /Al2.34Ni2.-40
tet
5Ni2.34Al6.-47
octa
%..
Another defected &'inel i& 89Al-%1
&ACT"RS A&&ECTIN' T(E STRUCTURE "& SPINELS
)# T*e relti%e si+es of A n, B$ In general, the &maller cation 'refer& to occu'( the
&ite of lo)er coordination i.e., tetrahedral &ite.
:o)ever, in the &'inel, MgAl-%. it&elf thi& factor i& out)eighed +( greater lattice energ( of
&maller cation, Al
1;
, )hich occu'ie& the octahedral &ite and thu& +( giving normal &'inel
&tructure. Otherwise the "spinel" will have the inverse spinel stucture!
2# T*e -,elun. constnts for t*e norml n, in%erse structures$ It i& o+&erved
that the Madelung con&tant& are &ame for +oth normal and inver&e &'inel& and hence are not
that much im'ortant in arriving at the &tructure.
/# Li.n,0&lel, St1ili+tion Ener.ies$ A''lica+le )henever there are tran&ition metal
ion& and i& di&cu&&ed +elo).
The &tructure& of &'inel& are affected +( the relative <F, value& of metal ion&. The ion
with more LFSE value in octahedral geometry when compared to the LFSE in
tetrahedral geometry tends to occupy octahedral sites.
The difference +et)een the <F, value& in octahedral and tetrahedral geometrie& i&
referred to a& %ctahedral ite ta+ili=ation ,nerg( /%,0.
If the B
III
ion has more CFSE gain in octahedral site than that of II ion! a
normal spinel is e"pected.#
$hereas an inverse spinel is formed whenever the divalent
II
ion has
comparatively more CFSE gain in octahedral geometry than the trivalent B
III
ion.#
S"-E 'ENERALI2ATI"NS RE'AR3IN' T(E STRUCTURES "& SPINELS
> A normal &'inel &tructure i& a&&umed if +oth the divalent and the trivalent metal& are
non tran&ition metal& &ince no CF, i& involved.
> There i& a tendenc( of formation of inver&e &'inel &tructure in &ome ca&e& /not all the
ca&e&0 )hich contain tran&ition metal ion&. Thi& i& +ecau&e, the tran&ition metal ion ma( get
e*tra &ta+ilit( /<F,0 in octahedral geometr(, 'refer& octahedral void& over tetrahedral one&.
> The d
2
? high &'in d
4
, d
62
ion& have no 'reference +et)een tetrahedral and octahedral
coordination &ince the <F, i& =ero.
> @&uall( d
1
A d
B
ion& have &tronge&t 'reference for octahedral geometr(.
> %ther ion& )ith d
6
, d
-
, d
.
, d
C
, d
3
, d
D
too have &lightl( more 'reference for octahedral
&(mmetr(.
> That mean&, if A
II
*s ,
/
or ,
4
confi.urtion and the !
III
ion ha& configuration other
than the&e, then the spinel is in%erte,.
> If the divalent A
II
i& a tran&ition metal /)ith configuration& other than d
2
? high&'in d
4
A
d
62
0 and the !
III
ion i& a non tran&ition metal, there i& a tendenc( to form inver&e &'inel.
!ut there are e*ce'tion& like FeAl-%. )hich ha& normal &'inel &tructure.
> A+ove generali=ation& are valid for high &'in &(&tem& a& the o*ide ion i& e*'ected to +e
a )eak field ligand.
For e*am'le, Co
1;
i& a lo) &'in &(&tem even in 're&ence of o*o ligand& due to high charge
on the ion.
A
II
B
III
Structure
Non tran&ition
metal
or
d
2
or d
4
or d
62
tran&ition metal
Non tran&ition
metal
'inel &tructure
Non tran&ition
metal
or
d
2
or d
4
or d
62
tran&ition metal
A tran&ition metal
)ith
d
6
or d
-
or d
1
or d
.
or d
C
or d
3
or
d
B
or d
D

configuration&
'inel &tructure
A tran&ition metal
)ith
d
6
or d
-
or d
1
or d
.
or d
C
or d
3
or
d
B
or d
D

configuration&
Non tran&ition
metal
or
tran&ition meta
)ith
d
2
or d
4
or d
62
configuration&
Inver&e &'inel
Tran&ition metal
)ith higher CF,
value
Tran&ition metal
)ith lo)er CF,
value
Inver&e &'inel
EXA-PLES &"R SPINEL AN3 INVERSE SPINEL STRUCTURES
60 -.Al2"4 is norml spinel &ince +oth the divalent and trivalent ion& are non
tran&ition metal ion&. There i& no Eue&tion of CF,.
-0 -n/"4 is norml spinel &ince the Mn
-;
ion i& a high &'in d
4
&(&tem )ith =ero <F,.
Wherea&, Mn
1;
ion i& a high &'in d
.
&(&tem )ith con&idera+le <F,.
10 &e/"4 is n in%erse spinel &ince the Fe/III0 ion i& a high &'in d
4
&(&tem )ith =ero
CF,. Wherea& the divalent Fe/II0 i& a high &'in d
C
&(&tem )ith more CF,.
.0 Ni&e2"4 is .in n in%erse spinel &ince the divalent Ni
-;
/a d
B
ion0 ha& more CF,
than the trivalent Fe
1;
/a d
4
ion0.
40 &eCr2"4 is norml spinel &ince the divalent Fe
-;
i& a high &'in d
C
ion )ith CF, = .
FE and the trivalent Cr
1;
i& a high &'in d
1
ion )ith CF, = 6- FE. :ence Cr
1;
get& more %,
)hile occu'(ing octahedral &ite&.
C0 Co/"4 is norml spinel. ,ven in the 're&ence of )eak field o*o ligand&, the Co
1;
i& a
lo) &'in d
C
ion )ith ver( high CF,. It i& due to high charge on Co
1;
. :ence all the Co
1;
ion&
occu'( the octahedral &ite&.
30 NiA)2"4 s*o5 rn,om or ,efecte, in%erse spinel. The CF, of Ni
II
i& greater in
octahedral than tetrahedral coordination. !ut Al
1;
al&o ha& &trong 'reference for octahedral
&ite& due to high lattice energ(. Thi& lead& to almo&t com'lete randomi=ation of all the cation&
on all the availa+le &ite&. It& formula can +e )ritten a& /Al2.34Ni2.-40
tet
5Ni2.34Al6.-47
octa
%..
ISOLOBAL ANALOGY
The clu&ter fragment& of molecule& are deemed to +e isolo1l if the( 'o&&e&& same
number of frontier molecular orbitals )ith:
i) similar shape, symmetry and radial extent;
ii) approximately the same energy;
iii) same number of electrons available for cluster bonding.
The i&olo+al fragment& may not be isostructural and isoelectronic. The( onl( 'o&&e&&
&imilar characteri&tic& for the frontier molecular or+ital&.
The relation +et)een i&olo+al fragment& i& indicated +( dou+le headed t)irl( arro)& i.e.,
)ith a tear9dro' / 0.
E6mples$
60 The C9: grou' /car+(ne0, G atom and Co/C%01 fragment are i&olo+al &ince the(
contri+ute 1 electron& for the clu&ter +onding.
-0 The !9: grou', the C:- grou' and Fe/C%01 fragment are i&olo+al to each other &ince
the( contri+ute - electron& for the clu&ter +onding.
Note$
, = no. of &keletal electron& contri+uted for clu&ter +onding.
In ca&e of tran&ition element&, the num+er of &keletal electron& contri+uted for clu&ter
+onding can +e calculated a& follo)&:
, = v ; * 9 6-
Where
v = no. of valence electron&
* = no. of electron& contri+uted +( ligand grou'&
'ENERATI"N "& IS"L"BAL &RA'-ENTS

We can al&o dra) the follo)ing i&olo+al analog( +et)een metal com'le*e& and organic
moeitie&.
APPLICATI"NS "& IS"L"BAL ANAL"'7
> Theoreticall( it i& 'o&&i+le to &u+&titute a fragment of a molecule +( another i&olo+al
fragment to generate a ne) molecule )ith ver( &imilar +onding.
:o)ever there i& no guarantee that the H'roductI of an i&olo+al tran&formation i& a&
&ta+le, kineticall( or thermod(namicall(, a& the HreactantI.
It ma( or ma( not +e 'o&&i+le to &(nthe&i=e the ne) molecule generated +( the i&olo+al
tran&formation.
,.g. A 'ho&'horu& atom in G. molecule can +e re'laced +( either 9C: grou' or 9Co/C%01.
JAHN TELLER DISTORTION (EFFECT) : THEOREM
8*n0Teller t*eorem$ In a nonlinear molecule! if degenerate or%itals are
asymmetrically occupied! a distortion will occur to remove the degeneracy.
!or#
In an electronically degenerate state! a nonlinear molecule undergoes distortion
to remove the degeneracy %y lowering the symmetry and thus %y lowering the
energy.
9*t is electronicll: ,e.enerte stte;
An electronicall( degenerate &tate re're&ent& the availa+ilit( of more than one degenerate
or+ital& for an electron. In thi& condition the degenerate or+ital& are a&(mmetricall( occu'ied.
,.g. In octahedral &(mmetr(, the d
6
configuration i& &aid to +e electronicall( degenerate
&ince three t-g or+ital& )ith &ame energ( are availa+le for the electron to occu'(. In thi&
condition, the degenerate or+ital& are al&o &aid to +e a&(mmetricall( occu'ied +( electron&.
Wherea& the d
1
configuration in octahedral geometr( i& non9degenerate and &(mmetric. It
i& not 'o&&i+le to 'ut t)o electron& in one or+ital, )hich i& again&t of :undJ& rule of ma*imum
multi'licit(.
8A(N TELLER 3IST"RTI"N $ EXPLANTI"N
> In the electronically degenerate state, the orbitals are said to be asymmetrically
occupied and get more energy. herefore the system tries to get rid of this extra energy by
lowering the overall symmetry of the molecule i.e., undergoing distortion, which is otherwise
!nown as &ahn Teller distortion.
,.g. In ca&e of octahedral d
D
configuration, the la&t electron ma( occu'( either d=- or d*-9
(- or+ital& of eg &et. If it occu'ie& d=- or+ital, mo&t of the electron den&it( )ill +e concentrated
+et)een the metal and the t)o ligand& on the = a*i&. Thu&, there )ill +e greater electro&tatic
re'ul&ion a&&ociated )ith the&e ligand& than )ith the other four on *( 'lane. Thi& a&(mmetric
di&tri+ution of the electron den&it( ma( increa&e the overall energ( of the &(&tem. To get rid of
thi&, the com'le* &uffer& elongation of +ond& on =9a*i& and thu& lo)er& the &(mmetr(.
Conver&el(, occu'ation of the d*-9(- or+ital )ould lead to elongation of +ond& along the *
and ( a*e&.
> The Kahn Teller di&tortion i& mo&tl( o+&erved in octahedral environment&. Theoreticall(
the electronic degenerac( in octahedral &(mmetr( i& 'o&&i+le in all the configuration& e*ce't
d
1
, d
B
, d
62
, high &'in d
4
and lo) &'in d
C
configuration&.
:o)ever con&idera+le di&tortion& are u&uall( o+&erved in *i.* spin ,
4
< lo5 spin ,
=
n,
,
>
configuration& in the octahedral environment. It i& +ecau&e the Kahn Teller di&tortion i&
u&uall( &ignificant for a&(mmetricall( occu'ied eg or+ital& &ince the( are directed to)ard& the
ligand& and the energ( gain i& con&idera+l( more.
> In ca&e of unevenl( occu'ied t-g or+ital&, the Kahn Teller di&tortion i& ver( )eak &ince the
t-g &et doe& not 'oint directl( at the ligand& and therefore the energ( gain i& much le&&.
,.g. d
6
? d
-
? lo) &'in d
.
A d
4
? high &'in d
3
A d
3
configuration&.
!ecau&e of &ame rea&on, the tetrahedral complexes also do not exhibit "ahn#eller
distortion. Again, in thi& ca&e al&o the ligand& are not 'ointing to)ard& the or+ital& directl(
and hence there i& le&& &ta+ili=ation to +e gained u'on di&tortion.

Note: The Kahn9Teller di&tortion in ca&e of lo) &'in d
B
octahedral &(&tem& to give &Euare 'lanar com'le*e& a&
e*'lained +( &ome author& i& controver&ial. Thi& )ill +e di&cu&&ed in later &ection&.
20"UT & 20IN 8A(N TELLER 3IST"RTI"NS
> The degenerac( of or+ital& can +e removed +( lo)ering the &(mmetr( of molecule. Thi&
can +e achieved +( either elongation of +ond& along the =9a*i& /Z9out di&tortion0 or +(
&hortening the +ond& along the =9a*i& /Z9in di&tortion0. Thu& an octahedrall( &(mmetrical
molecule i& di&torted to tetragonal geometr(.
20out ,istortion$ In thi& ca&e, the energie& of d9or+ital& )ith = factor / i.e., d=-, d*=, d(= 0
are lowered &ince the +ond& along the =9a*i& are elongated. Thi& i& the mo&t 'referred
di&tortion and occur& in mo&t of the ca&e&, e&'eciall( )hen the degenerac( occur& in eg level.
,.g. @&uall( the octahedral d
-
, d
.
high &'in, d
3
lo) &'in, d
B
lo) &'in A d
D
configuration&
&ho) the =9out di&tortion.
Theoreticall( it i& not 'o&&i+le to 'redict the t('e of di&tortion occur& )hen the degenerac(
occur& in eg level. :o)ever it i& o+&erved that =9out di&tortion i& more 'referred.
20in ,istortion$ In thi& ca&e the energie& of or+ital& )ith = factor are increased &ince the
+ond& along the =9a*i& are &hortened. Thi& t('e of di&tortion i& o+&erved in ca&e of octahedral
d
6
configuration. The onl( electron )ill no) occu'( the d*( or+ital )ith lo)er energ(.
,.g. The octahedral d
6
configuration& like Ti/III0 in 5Ti/:-%0C7
1;
&ho) =9in di&tortion. In thi&
ca&e, the =9out di&tortion do not remove the degenerac( &ince even after di&tortion there are
&till t)o degenerate or+ital& i.e., d*= and d(= availa+le for the electron to occu'(. ee the
follo)ing diagram.
Al&o remem+er that the Kahn9Teller theorem doe& N%T 'redict ho) large a di&tortion
&hould occur.
STATIC & 37NA-IC 8A(N0TELLER 3IST"RTI"NS
Sttic 8*n0Teller ,istortion$ ome molecule& &ho) tetragonal &ha'e under all
condition& i.e., in &olid &tate and in &olution &tate? at lo)er and relativel( higher tem'erature&.
Thi& i& referred to a& &tatic Kahn9Teller di&tortion. It i& o+&erved )hen the degenerac( occur& in
eg or+ital&. :ence the di&tortion i& &trong and 'ermanent.
3:nmic 8*n0Teller ,istortion$ In &ome molecule&, the di&tortion i& not &een either
due to random movement& of +ond& )hich doe& not allo) the mea&urement )ithin a time
frame or el&e the di&tortion i& &o )eak a& to +e negligi+le. :o)ever the di&tortion can +e &een
+( free=ing the molecule at lo)er tem'erature&. Thi& condition i& referred to a& d(namic Kahn9
Teller di&tortion.
,.g.
60 The com'le*e& of the t('e M-G+Cu/N%-0C &ho) d(namic Kahn9Teller di&tortion.
:ere, M= L, M+, C&, Tl?
The( &ho) tetragonal &(mmetr( at lo)er tem'erature& due to &tatic Kahn9Teller di&tortion.
!ut at higher tem'erature&, the&e molecule& a''ear octahedral due to the d(namic Kahn9Teller
effect.
-0 The com'le* 5Fe/:-%0C7
-;
&ho)& d(namic Kahn9Teller di&tortion and a''ear& octahedral.
In thi& ca&e, the di&tortion i& &mall &ince the degenerac( occur& in t-g or+ital&. Memem+er Fe
-;
in a+ove com'le* i& a high &'in d
C
&(&tem )ith t-g
.
eg
-
configuration.
A C"NTR"VERS7
According to one &chool of thought, the com'le*e& formed +( lo) &'in d
B
&(&tem&, like
Ni/II0, are electronicall( degenerate in the octahedral environment &ince the &trong field
ligand& around the metal ion force the t)o electron& in the eg or+ital& to 'air u'. :ence the(
al&o undergo the Kahn Teller di&tortion +( com'letel( eliminating the ligand& on the =9a*i& to
+ecome &Euare 'lanar.
,.g. 5Ni/CN0.7
-9
i& a &Euare 'lanar com'le*.
The &ame argument& are al&o a''lica+le to the &Euare 'lanar com'le*e& formed +( Gt, Gd
etc.
After the picture
!ut thi& argument i& de+ata+le &ince the pairing of electrons is against the $und%s rule.
According to another &chool of thought, the lo) &'in d
B
&(&tem& are not at all electronicall(
degenerate in the octahedral environment. Therefore no Eue&tion of Kahn9Teller di&tortion.
The( e*hi+it &Euare 'lanar geometr( &im'l( +ecau&e the cr(&tal field &'litting energ(, N in thi&
geometr( i& ver( high &ince the ligand& are of &trong field. Thi& )ill al&o increa&e& the CF,
value.
The &Euare 'lanar geometr( i& thought to +e re&ulted due to infinite di&tortion of
octahedral geometr( along the =9a*i& /&ee the diagram +elo)0. $owever this is not the "ahn#
eller distortion. Wh(O !ecau&e, the octahedral d
B
i& N%T electronicall( degenerate.

%n the other hand, the high &'in Ni/II0 com'le*e&, like NiCl .
-9
, are tetrahedral. It i&
+ecau&e the N value in 're&ence of )eak field ligand& i& lo) and doe& not favor the &Euare
'lanar geometr(. It& geometr( i& tetrahedral +ecau&e in thi& configuration, the ligand& are
'laced a& far a)a( a& 'o&&i+le from each other.
!ut all t('e& of com'le*e& of Gt, Gd? irre&'ective of )hether the( are high &'in or lo) &'in,
are &Euare 'lanar.
The rea&on& are:
60 A& )e move do)n the grou', the N value increa&e& +( a+out 42P in all ca&e&.
-0 <igand re'lul&ion& are minimi=ed due to large &i=e of the metal. Thi& favor& &Euare
'lanar geometr(.
10 Fue to the 9interaction& of d9or+ital& of metal& )ith the or+ital& of ligand& the &ta+ilit(
of &Euare 'lanar geometr( increa&e&.
Note: :o)ever the 9interation& are not 'o&&i+le in ca&e of Ni/II0 due to &mall &i=e of it&
d9or+ital& /no effective overla''ing0.
C"NSE?UENCES & ILLUSTRATI"NS "& 8A(N TELLER E&&ECT
)# 8*n0Teller ,istortion in comple6es forme, 1: Cu!II# ions$
# Tetr.onl structure of Cu!II# comple6es$ The Cu/II0 ion i& a d
D
&(&tem and
e*'ected to &ho) Kahn9Teller di&tortion and u&uall( de'art con&idera+l( from octahedral
geometr(. The Cu/II0 ion in the aEueou& medium i& &urrounded +( &i* )ater molecule& in
tetragonal geometr( i.e., four of )hich are at the corner& of &Euare 'lane and are at &horter
di&tance& )ith &tronger interaction&, )herea&, the remaining t)o are )eakl( interacting )ith
the metal ion at di&tant a*ial 'o&ition&.
1# Structure of *:,rte, copper!II# sulp*te< CuS"4@A(2" n, ot*er Cu!II#
comple6es$ In the &olid Cu%..4:-%, the co''er ion i& &urrounded +( four )ater molecule& in
&Euare 'lanar geometr(. There are al&o )eak interaction& )ith the &ul'hate ion& in the a*ial
'o&ition&. The 4th )ater molecule i& h(drogen +onded to the &ul'hate ion. That mean& the t)o
)ater molecule& on the a*ial 'o&ition& are com'letel( eliminated and &u+&tituted +( &ul'hate
ion& )hile forming the &olid.
Note: Fue to interaction& )ith the&e ligand&, the d or+ital& are &'lit into different
energ( level&, )hich make& d9d tran&ition& 'o&&i+le. It a+&or+& red color and
tran&mit& +lue color during the d9d tran&ition. !ut u'on heating, all the )ater
molecule& are lo&t, )hich make& all the d or+ital& degenerate again. :ence the
anh(drou& Cu%. i& colorle&&.
c# E6tr st1ilit: of Cu
2B
ions$ The relative &ta+ilitie& of com'le*e& formed +( high &'in
divalent fir&t ro) tran&ition metal ion& i& given +( Irving9William& &erie&. The &ta+ilit( order i&
&ho)n +elo):
Mn/II0 Q Fe/II0 Q Co/II0 Q Ni/II0 Q Cu/II0 R Zn/II0
The e*tra &ta+ilit( of Cu/II0 ion can +e e*'lained +( taking into account of Kahn9Teller
di&tortion of thi& d
D
ion.
,# "t*er e6mples$ !ecau&e of Kahn9Teller di&tortion:
> In the cr(&talline LCuF1, the t)o Cu9 F di&tance& are at 6.DC A
2
and the remaining four
Cu 9 F di&tance& are at -.23 A
2
. It i& a ca&e of Z9com're&&ion.
> In 5Cu/hfacac0-/+i'(07, there are t)o &hort Cu9% +ond& and t)o long CuS% +ond&.
/)here hfacac = he*afluoroacet(lacetone anion? +i'( = -,-T9+i'(ridine0. It i& an e*am'le for
Z9out di&tortion.
> Cu/II0 cannot form 5Cu/en017
-;
&ince KT di&tortion +ring& &train into the eth(lene diamine
molecule that i& added along =9a*i&. :ence onl( 5Cu/en0-/:-%0-7
-;
i& formed.
2# T*e splittin. of 1sorption 1n,s in t*e UV0VIS spectr of comple6es ,ue to
8*n0Teller ,istortion$
,.g. The a+&or'tion +and in the electronic &'ectrum of aEueou& Ti/III0, a d
6
octahedral
&(&tem, i& not &(mmetric +ut rather &ho)& a di&tinct +road &houlder. It i& +ecau&e of Kahn9
Teller di&tortion.
The Kahn9Teller di&tortion i& negligi+le in ca&e of degenerate t-g or+ital& in the ground
&tate. :ence no di&tortion in the ground &tate. !ut )hen the electron get& e*cited, the
configuration no) +ecome& t-g
2
eg
6
, )hich i& again degenerate. :ence in the e*cited &tate, the
Kahn Teller di&tortion i& 'o&&i+le. No) the 'romotion of electron ma( occur to either of the t)o
non degenerate eg or+ital&, the d=- and d*-9(-. Thu&, t)o tran&ition& are 'o&&i+le. !ut a
&houlder a''ear& &ince the energ( difference +et)een t)o tran&ition& i& &mall.
/# Coor,inti%el: l1ile nture of CCr!(2"#DE
2B
& CCo!N(/#DE
2B
$
The 5Cr/:-%0C7
-;
undergoe& &u+&titution ea&il( &ince the Cr/II0 ion i& a high &'in d
.
&(&tem
)ith one electron in the eg or+ital. :ence it i& electronicall( degenerate and &ho)& Kahn9Teller
di&tortion. :ence the h(drated Cr/II0 ion i& coordinativel( la+ile.
%n the &ame line&, the ea&( &u+&titution of 5Co/N:10C7
-;
+( )ater molecule& can +e
e*'lained. In thi& ca&e the Co/II0 ion i& coordinativel( la+ile &ince it i& a lo) &'in octahedral d
3
ion )hich i& degenerate in eg &et. :ence it undergoe& K9T di&tortion and i& la+ile.
4# 3isproportiontion of Au!II# slts$
Au/II0 ion i& le&& &ta+le and undergoe& di&'ro'ortionation to Au/I0 and Au/III0 even
though the Cu/II0 and Ag/II0 ion& are com'arativel( more &ta+le. %ne ma( e*'ect &ame
&ta+ilit( &ince all are d
D
&(&tem& and undergo the Kahn9Teller di&tortion.
:o)ever, the N value increa&e do)n the grou'. :ence, in Au/II0 ion, it reache& a
ma*imum, )hich cau&e& high de&ta+ili=ation of the la&t electron, )hich i& no) occu'(ing the
d*-9(-. Thi& make& Au/II0 reactive, )hich ma( undergo either o*idation to Au/III0, a d
B
&(&tem
or reduction to Au/I0, a d
62
&(&tem.
The d
B
&(&tem, Au/III0 i& &ta+le a& the electron from the d*-9(- i& removed. Mo&tl( it
'refer& &Euare 'lanar geometr( and more &ta+le than +oth Au/II0 and Au/I0. The d
62
&(&tem,
Au/I0 favor& mo&tl( linear geometr( )ith coordination num+er = -.
Wh( do the d
D
&(&tem& u&uall( not undergo com'lete di&tortion to &Euare 'lanar
geometr(O
An&: @&uall(, the d
D
&(&tem& are tetragonal )ith elongated +ond& on =9a*i& and
do not undergo com'lete di&tortion to &Euare 'lanar. It i& +ecau&e the la&t electron
)ill +e 'laced in highl( de&ta+ili=ed d*-9(- if the( get &Euare 'lanar geometr(. !ut the
lo) &'in d
B
com'le*e& ma( undergo com'lete di&tortion to &Euare 'lanar geometr(.
PEARSON'S HARD & SOFT ACIDS & BASES (HSAB) THEORY
(r, n, Soft Aci,s n, Bses !(SAB# T*eor: i& a Eualitative conce't introduced +(
Mal'h Gear&on to e*'lain the &ta+ilit( of metal com'le*e& and the mechani&m& of their
reaction&.
:o)ever it i& 'o&&i+le to Euantif( thi& conce't +a&ed on Llo'manJ& FM% anal(&i& u&ing
interaction& +et)een :%M% and <@M%.
According to thi& theor(, the <e)i& acid and +a&e& can +e further divided into hard or &oft
or +order line.
(r, Le5is ci,s are characteri=ed +( &mall ionic radii, high 'o&itive charge, &trongl(
&olvated, em't( or+ital& in the valence &hell and )ith high energ( <@M%&.
Soft Le5is ci,s are characteri=ed +( large ionic radii, lo) 'o&itive charge, com'letel(
filled atomic or+ital& and )ith lo) energ( <@M%&.
(r, Le5is 1ses are characteri=ed +( &mall ionic radii, &trongl( &olvated, highl(
electronegative, )eakl( 'olari=a+le and )ith high energ( :%M%&.
Soft Le5is 1ses are characteri=ed +( large ionic radii, intermediate electronegativit(,
highl( 'olari=a+le and )ith lo) energ( :%M%&.
The Bor,er line <e)i& acid& and +a&e& have intermediate 'ro'ertie&.
Memem+er that it i& not nece&&ar( for <e)i& acid or +a&e to 'o&&e&& all the 'ro'ertie& to
+e cla&&ified a& hard or &oft or +orderline.
'SB (rinciple) &ccording to $'&( concept, hard acids prefer binding to the hard bases
to give ionic complexes, whereas the soft acids prefer binding to soft bases to give covalent
complexes.
According to FM% anal(&i&, the interaction& +et)een acid& and +a&e& are controlled +( the
relative energie& of the 'artici'ating frontier molecular or+ital& /FM%0 i.e., :%M% and <@M%.
C(ARACTERISTICS "& (AR3< S"&T & B"R3ERLINE ACI3S & BASES
T:pe of
Aci,FBse
C(ARACTERISTICS EXA-PLES
(r, ci,s
> Atomic centre& of
&mall ionic radiu&.
> :igh 'o&itive
charge.
> ,m't( or+ital& in
their valence &hell&.
> <o) electron
affinit(.
> <ikel( to +e
&trongl( &olvated.
> :igh energ( <@M%.
:
;
, <i
;
, Na
;
, L
;
, !e
-;
, Mg
-;
, Ca
-;
, r
-;
, n
-;
Al
1;
, "a
1;
, In
1;
, Cr
1;
, Co
1;
, Fe
1;
, Ir
1;
, <a
1;
, i
.;
,
Ti
.;
, Zr
.;
, Th
.;
, #%
-;
, @%-
-;
!eMe-, !F1, !Cl1, !/%M01, AlMe1
Soft ci,s
> <arge radiu&.
> <o) or 'artial
'o&itive charge.
> Com'letel( filled
or+ital& in their
valence &hell&.
> <o) energ(
<@M%J& )ith large
magnitude of <@M%
coefficient&.
Cu
;
, Ag
;
, Au
;
, :g
;
, C&
;
, Tl
;
, :g
-;
, Gd
-;
, Cd
-;
,
Gt
-;

Metal atom& in =ero o*idation &tate&
Bor,er
line ci,s

Fe
-;
, Co
-;
, Ni
-;
, Cu
-;
, Zn
-;
, G+
-;
, !/C:101, %-,
N%
;
(r,
1ses
> mall A highl(
&olvated.
> electronegative
atomic centre& /1.29
..20.
> Weakl( 'olari=a+le.
> Fifficult to +e
o*idi=ed.
> :igh energ(
:%M%.
:-%, %:
9
, F
9
, Cl
9
, C:1C%-9, G%.
19
, %.
-9
, C%1
-9
, N%1
9
,
Cl%.
9
, M%:, M%
9
, M-%, N:1, MN:-, N-:.
Soft 1ses
> <arge atom& of
intermediate
electronegativit(
/-.491.20.
> :igh 'olari=a+ilit(
> ,a&il( undergo
o*idation.
> <o) energ(
:%M%J& +ut large
magnitude :%M%
coefficient&.
M:, M
9
, M-, I
9
, CN
9
, CN
9
, -%1
9
, M1G, M1A&
/M%01G, MNC, C%, C-:., CC:C, M
9
, :
9
Bor,er
line 1ses
Aniline, '(ridine, N1
9
, !r
9
, N%-
9
, %1
-9
, N-
APPLICATI"NS "& (SAB PRINCIPLE
In *:,ro.en 1on,in.$ The &trong h(drogen +ond i& 'o&&i+le in ca&e& of :-%, N:1 and
:F, &ince the donor atom& /F, % A N0 are hard le)i +a&e& and their interaction& )ith 'artiall(
'o&itivel( charged :, )hich i& a hard acid are &tronger.
LinG.e of m1i,entte li.n,s to metl toms$ The am+identate ligand, CN
9
can
+ind either +( end or N end. The +onding mode can +e determined +( u&ing :A! 'rinci'le.
It +ond& through &ulfur atom /&oft +a&e0 )hen +onded to Gt
-;
, a &oft acid.
:o)ever it +ond& through nitrogen atom /a hard +a&e0 )hen linked to Cr
1;
, a hard acid.
Site preference in or.nic rections$ MC%$ i& a hard acid and react& )ith the nitrogen
end of CN
9
ion to form an ac(l i&othioc(anate.
Wherea& the &ofter meth(l grou' +ond& to the ulfur atom and form& meth(l thioc(anate.

Inor.nic rections$ :A! 'rinci'le i& u&ed to 'redict the outcome of &ome of the
reaction&.
60 The follo)ing reaction i& 'o&&i+le +ecau&e A& i& &ofter than and I
9
i& &ofter than F
9
.
Memem+er that +oth A& and are &oft +ut relativel( A& i& &ofter.
-0 The follo)ing reaction i& 'o&&i+le &ince Mg
-;
i& harder acid than !a
-;
and %
-9
i& harder
+a&e than
-9
.
Precipittion rections$ The &ofter acid& like Ag
;
, :g
;
, :g
-;
etc., and +order line acid&
like Fe
-;
, Ni
-;
, Cu
-;
, Zn
-;
, G+
-;
etc., can +e 'reci'itated a& &ulfide& from their aEueou&
&olution& &ince
-9
ion i& a &ofter +a&e.
TRANS E&&ECT
It i& o+&erved that during the &u+&titution reaction& of &Euare 'lanar metal com'le*e&,
&ome ligand& 'referentiall( direct the &u+&titution trns to them&elve&. i.e., the choice of
leaving grou' i& determined +( the nature of ligand tran& to it.
he Trans effect can be defined as the effect of a ligand over rate of substitution of
another ligand positioned trans to it in the s)uare planar complexes.
JTJ i& the tran& directing grou' and JNuJ i& the nucleo'hilic ligand )hich 'referentiall(
&u+&titute& the ligand J$J )hich i& tran& to ligand JTJ.
> The Tran& effect )a& fir&t recogni=ed +( Il(a Ilich Chern(aev, a ru&&ian chemi&t in &Euare
'lanar com'le*e& of Glatinum/II0.
> :o)ever the Tran& effect i& al&o o+&erved in octahedral com'le*e&.
> The true Tran& effect i& a kinetic effect.
3I&&ERENCE BET9EEN TRANS IN&LUENCE AN3 TRANS E&&ECT
In general there are t)o factor& contri+uting to tran& direction of &u+&titution a& de&cri+ed
+elo):
)# Trns influence$ Thi& i& a thermod(namic factor. ome ligand& )eaken the M9< +ond
tran& to them in the ground state and thu& +( facilitating the &u+&titution.
,.g. trong U9 donor& like :
9
, I
9
, Me
9
, GM1 etc., de&ta+ili=e the M9< +ond tran& to them&elve&
and thu& +( +ringing the ea&( &u+&titution of that ligand.
2# Trns effect$ Thi& i& a kinetic factor and con&idered a& true tran& effect. It occur& +(
the &ta+ili=ation of the tran&ition &tate.
,.g. The &trong 9acce'tor& like N%
;
, C-:., C%, CN
9
etc., &ta+ili=e the transition state +(
acce'ting electron den&it( that the incoming nucleo'hilic ligand donate& to the metal through
9interaction.
Note: Thi& i& de+ata+le &ince the 9interaction ma( increa&e the &trength of M9< +ond
e&'eciall( in the tran& 'o&ition.
-EC(ANIS- "& TRANS E&&ECT
Hinetic stu,ies$ Mo&t of the kinetic )ork i& done on &Euare 'lanar Gt/II0 com'le*e& to
monitor the tran& effect during the &u+&titution reaction&. The kinetic &tudie& indicate the
a&&ociative mechani&m a& de&cri+ed +elo).
> !oth N
V
and N#
V
are negative indicating the a&&ociative mechani&m, either A or Ia.
Where:
N
V
= ,ntro'( of activation
N#
V
= Change in volume )hile forming the tran&ition &tate from the reactant&.
A negative N#
V
corre&'ond& to the tran&ition &tate +eing com're&&ed relative to the
reactant&. The volume of tran&ition &tate i& le&& than the com+ined volume of the reactant&.
> The e*'erimentall( o+&erved rate la) for a &Euare 'lanar &u+&titution reaction?
M<-T$ ; Nu 999999R M<-TNu ; $
can +e )ritten a&:
rate * !+,-./01 2 !/,-./01,3u1
Where:
T = tran& directing ligand,
$ = ligand 'o&itioned tran& to T.
Nu = Nucleo'hile
The de'endence of rate on the concentration of Nu indicate& the a&&ociative mechani&m.
> The &tereo chemical retention of configuration i& o+&erved during &u+&titution.
> In &ome ca&e& the 4 or C coordinated &'ecie& are i&olated during the reaction.
> Gre&ence of +ulk( grou'& on the metal com'le*e& decrea&e the rate of &u+&titution. It
indicate& again the a&&ociative mechani&m.
-ec*nism$
The a+ove kinetic data along )ith 'referential &u+&titution at tran& 'o&ition of certain
ligand& &ugge&t the 'o&&i+le formation of 4#coordinate trigonal planar transition state 5or
intermediate).
Wh( the tran& &u+&titution i& favoredO
In the 49coordinate Trigonal +i'(ramidal tran&ition &tate, the electro&tatic re'ul&ion i&
decrea&ed due to removal of electron den&it( in the eEuatorial 'lane. The removal of electron
den&it( if facilitated +( the 9interaction of the tran& directing ligand, T a& &ho)n +elo).
> The &Euare 'lanar &u+&titution reaction& occur &lo)l( due to lo&& of CF, during the
formation of trigonal +i'(ramidal com'le* from &Euare 'lanar one. The lo&& of CF, i&
increa&ed do)n the grou'. :ence the &Euare 'lanar &u+&titution& of .d and 4d &erie& are
&lo)er. Thi& i& )h( mo&t of the &Euare 'lanar &u+&titution kinetic &tudie& are done on Gt/II0
com'le*e&.
> The rough order of tran&9directing effect of variou& ligand& i&:
N%
;
, C%, CN
9
, C-:. R GM1, :
9
R Me
9
R Gh
9
R N%-
9
, I
9
, CN
9
R !r
9
R Cl
9
R G(, N:1, %:
9
, :-%
ILLUSTRATI"NS "& TRANS E&&ECT
The Tran& effect can dictate the 'roduct formed in the &u+&titution reaction&. The cla&&ic
e*am'le of Tran& effect i& the &(nthe&i& of cispltin, ci&9diamminedichlorido'latinum/II0. It i&
're'ared +( &u+&tituting the t)o chloro grou'& of GtCl.
-9
+( ammonia molecule&.
In the fir&t &te', an( of the chloro grou' i& &u+&tituted +( ammonia randoml(. !ut in the
&econd &te', the ammonia grou' 'referentiall( &u+&titute& the chloro grou' ci& to the fir&t
ammonia. Thi& can +e attri+uted to the fact that the Cl
9
ha& a larger tran& effect than N:1.
Wherea&, the tran& 'roduct i& o+tained +( &tarting from Gt/N:10.
-;
. In thi& ca&e the &econd
Cl grou' i& &u+&tituted 'referentiall( at tran& 'o&ition to the fir&t one.
Peric:clic rections are the concerted reaction& involving reorgani=ation of electron&
)hich occur +( the )a( of a &ingle cyclic transition state.
C*rcteristics of Peric:clic rections$
> The 'eric(clic reaction& occur in &ingle &te' and hence there i& no intermediate formed
during the reaction.
> The +reaking and making of +ond& /+oth U A 0 occur &imultaneou&l( in a c(clic
tran&ition &tate.
> The configuration of the 'roduct de'end& on
60 the configuration of reactant&
-0 the num+er of electron 'air& undergoing reorgani=ation and
10 the reaction condition& /like thermal or 'hotochemical0.
T7PES "& PERIC7CLIC REACTI"NS
The 'eric(clic reaction& are further cla&&ified into follo)ing t('e&:
60 C(cloaddition reaction& -0 ,lectroc(clic reaction&
10 igmatro'ic rearrangement& .0 "rou' tran&fer reaction&
40 Cheletro'ic reaction& C0 F(otro'ic rearrangement&
C7CL"A33ITI"N REACTI"NS
C:clo,,ition rections involve the formation of a c(clic 'roduct due to addition of t)o
different +ond containing com'onent&, )hich are Woined +( ne)l( formed t)o U +ond& at
their end& at the e*'en&e of t)o +ond&.
It i& u&uall( rever&i+le and the +ack)ard reaction i& al&o referred to a& retro9c(cloaddition
or a c(clorever&ion.
The cla&&ic e*am'le of c(cloaddition i& Fiel&9Alder reaction +et)een a Fiene and a
Fieno'hile to give a c(clic adduct.
3ote6 he direction of curly arrows have no significance here. he movement of electrons
can be shown either cloc!wise or anti cloc!wise.
ELECTR"C7CLIC REACTI"NS
Electroc:clic rections are intramolecular 'eric(clic reaction& )hich involve the
rearrangement of -electron& in an o'en conWugated &(&tem leading to formation of a c(clic
'roduct )ith a ne) U +ond at the e*'en&e of a -+ond.
:o)ever the electroc(clic reaction& not onl( involve ring9clo&ure +ut al&o ring o'ening,
)hich are referred to a& retro9electroc(clic reaction&.
,.g. The formation of C(clohe*a96,19diene +( heating :e*a96,1,49triene i& an e*am'le of
ring9clo&ure electroc(clic reaction.
SI'-ATR"PIC REARRAN'E-ENTS
Si.mtropic rerrn.ements are concerted unimolecular i&omeri=ation reaction&
characteri=ed +( the overall movement of a U9+ond from one 'o&ition to another )ith an
accom'an(ing rearrangement of -electron& of conWugated &(&tem &o a& to accommodate the
ne) U9+ond.
,.g. The 51,17 Co'e rearrangement. The U9+ond undergoing movement i& &ho)n a& red
thick line.
Note: Though looking like electroc(clic reaction&, there i& no reduction in the num+er of -
+ond& in &igmatro'ic reaction&.
'R"UP TRANS&ER REACTI"NS
The concerted tran&fer of a grou' from one molecule to another due to concomitant
movement of a U9+ond /from one molecule to another0 and formation of a ne) U9+ond
/+et)een t)o molecule&0 at the e*'en&e of a -+ond i& generall( referred to a& .roup
trnsfer 'eric(clic reaction.
,.g. The ,ne reaction +et)een 'ro'ene and ethene to give 69'entene i& a cla&&ic e*am'le
of grou' tran&fer reaction.
The&e reaction& re&em+le &igmatro'ic rearrangement&, &ince a U9+ond move&. :o)ever
&igmatro'ic reaction& are unimolecular reaction& )herea& the grou' tran&fer reaction& are
+imolecular.
The( al&o re&em+le c(cloaddition&, &ince a ne) U9+ond i& formed at the e*'en&e of a -
+ond. :o)ever, in grou' tran&fer reaction&, no ring i& formed.
C(ELETR"PIC REACTI"NS
C*eletropic rections are a &'ecial cla&& of c(cloaddition& or retro9c(cloaddition& in
)hich the t)o U9+ond& are either made or +roken to the &ame atom.
,.g. The rever&i+le addition of &ulfur dio*ide to 6,19+utadiene i& an e*am'le of cheletro'ic
reaction, in )hich the t)o ne) U9+ond& /&ho)n in red0 are made to the &ulfur atom.

Note: In thi& reaction, a lone 'air on &ulfur atom i& eEuivalent a -+ond and i&
reorgani=ed. %ne -+ond and a lone 'air are di&a''eared, )herea& t)o U9+ond& are formed.
Al&o note that &ulfur atom i& o*idi=ed from ;. to ;C &tate.
37"TR"PIC REARRAN'E-ENTS
The 'eric(clic reaction& )hich involve concerted intramolecular migration of t)o U9+ond&
&imultaneou&l( are kno)n a& ,:otropic rerrn.ements.
:o)ever d(otro'ic reaction& can al&o occur &te')i&e.
There are t)o t('e& of d(otro'ic rearrangement&:
T:pe0I$ T)o migrating grou'& interchange their relative 'o&ition&

T:pe0II$ The U9+ond& are migrated to ne) +onding &ite& )ithout an( 'o&itional
interchange for grou'&.
C"-PARIS"N "& 3I&&ERENT T7PES "& PERIC7CLIC REACTI"NS
All t('e& of 'eric(clic reaction& are concerted and involve c(clic tran&ition &tate )ithout
an( intermediate formed during the reaction. The characteri&tic& )hich differentiate them from
each other are ta+ulated +elo).
S@no
T:pe of peric:clic
rection
c*n.e in
no@ of
I 1on,s
c*n.e in
no@ of
1on,s
comments
)# C:clo,,ition
rections
;- 9- A c(clic 'roduct i& formed?
ma( +e intermolecular or
intramolecular.
2#
Electroc:clic
rections
;6 96 Intramolecular.
/#
Si.mtropic
rections
2 2
Intramolecular?
migration of a U9+ond?
rearrangement of -electron&
4#
'roup trnsfer
rections
;6 96
Intermolecular tran&fer of a grou'?
migration of a U9+ond from one
molecule to another?
formation of ne) U9+ond at the
e*'en&e of one 9+ond.
A#
C*eletropic
rections
;-
96 /9+ond0
96 /lone 'air0
A c(clic 'roduct i& formed?
t)o U9+ond& are formed to &ame
atom?
A lone 'air i& di&a''eared.
D# 3:otropic rections 2 2
imultaneou& migration of t)o U9
+ond&.
REACTI"N C"N3ITI"NS &"R PERIC7CLIC REACTI"NS
It i& o+&erved that &ome of the 'eric(clic reaction& occur onl( u'on heating, )herea& the
other are 'o&&i+le onl( under 'hotochemical condition&.
,.g. The Fiel&9Alder reaction, a 5.;-7 c(cloaddition occur& under thermochemical
condition& and i& not 'o&&i+le under 'hotochemical condition&.
Wherea& the follo)ing 5-;-7 c(cloaddition i& for+idden under thermal condition&. !ut the
reaction i& 'o&&i+le under 'hotochemical condition&.
,ven though, mo&t of the time&, the final 'roduct& are thermod(namicall( &ta+le, there i&
a high kinetic +arrier due to &(mmetr( con&ideration& under 'articular condition& to make the
reaction for+idden. :o)ever the &ame &(mmetr( con&ideration& allo)ed the reaction in
different condition&.
&R"NTIER -"LECULAR "RBITAL !&-"# T(E"R7
Frontier Molecular %r+ital /FM%0 theor( 'ro'o&ed +( Lenichi Fukui in 6D4-, e*'lain&
)hether a 'eric(clic reaction i& allo)ed or not under given &et of reaction& condition& +a&ed on
interaction& +et)een frontier molecular or+ital& /FM%&0 like :%M%, <@M% A %M%.
:%M% = :ighl( %ccu'ied Molecular %r+ital
<@M% = <o)e&t @noccu'ied Molecular %r+ital
%M% = ingl( %ccu'ied Molecular %r+ital
The interaction +et)een one FM% of one molecule )ith one FM% of another molecule
re&ult& in t)o t('e& of ne) Molecular %r+ital& /M%&0 i.e., +onding and anti+onding. The
+onding or+ital& 'o&&e&& lo) energ(, )herea& the anti+onding or+ital& 'o&&e&& higher energ(.
If +oth of the&e re&ulting M%& are filled )ith electron&, the +onding interaction i& cancelled
+( the anti +onding interaction. :ence the net re&ult i& no 1on,in. +et)een molecule&.
:o)ever, if onl( +onding or+ital& are filled )ith electron&, the t)o molecule& ttrct )ith
each other.
> Interaction +et)een :%M% A :%M% cau&e& re'ul&ion i.e., no +onding interaction &ince
+oth +onding and anti+onding M%& are filled )ith electron&.
> Interaction +et)een :%M% A <@M% cau&e& attraction i.e., +onding interaction, &ince onl(
the +onding M% i& filled )ith electron&.
> Interaction +et)een <@M% A <@M% cau&e& neither attraction nor re'ul&ion &ince all the
re&ulting M%& are em't(.
> Interaction of %M% )ith either :%M% or <@M% or another %M% al&o cau&e& attraction
+et)een the interacting &'ecie&.
The effect& of interaction& +et)een frontier molecular or+ital& i& &ummari=ed in the
follo)ing ta+le.
Interctin.
&rontier -oleculr "r1itls
T:pe of Interction
:%M% ; :%M% No +onding
:%M% ; <@M% Attraction 9 !onding
<@M% ; <@M% No electron&, null interaction 9 No +onding
%M% ; :%M%
%M% ; <@M%
%M% ; %M%
Attraction 9 !onding
9""39AR30("&&-ANN RULES
To 'redict )hether a 'eric(clic reaction i& allo)ed or not under given condition, Wood)ard
and :offmann 'ro'o&ed follo)ing &et of rule& +a&ed on conservation of orbital symmetry
conce't.
thermal pericyclic reaction is allowed in the ground state! when the total
num%er of *+, - ./s and *+r/a components is odd.
0therwise! if the total of *+, - ./s and *+r/a components is even! the pericyclic
reaction is allowed in the e"cited state i.e.! under photochemical conditions.

Num1er of !4J B 2#s n, !4r#
components
T*e con,ition un,er 5*ic* t*e rection is
llo5e,
o,, Thermal
e%en Ghotochemical
Component$ A +ond/&0 or an or+ital/&0 taking 'art in the 'eric(clic reaction a& a &ingle
unit can +e con&idered a& a com'onent. It can have an( num+er of electron& +ut ma( not
have mi*ture& of and U electron&.
,.g.
A dou+le +ond i& con&idered a& a - com'onent, &ince there are t)o electron&.
A conWugated diene can +e con&idered a& . com'onent, &ince there are four
electron&.
KsK re're&ent& suprfcil. A &u'rafacial com'onent form& ne) +ond& on the &ame face
at it& +oth end&. In &ome ca&e& &u'rafacial i& eEuivalent to Xdi&9rotationX.
KK re're&ent& ntrfcil. An antarafacial com'onent form& ne) +ond& on the o''o&ite
face& of it& +oth end&. In &ome ca&e& antarafacial i& eEuivalent to Xcon9rotationX.
,.g.
-& re're&ent& a com'onent containing t)o electron& and forming ne) +ond& in
&u'rafacial manner.
.a re're&ent& a com'onent containing four electron& and i& going to form ne)
+ond& in antarafacial manner.
J & r$ The&e are integer&.
!4J B 2#s component$ The &u'rafacial com'onent, )hich ma( have either - or C or 62 or
Y Y Y electron& of &ame t('e. The&e num+er& are o+tained +( &u+&tituting JEJ +( 2 or 6 or - or
Y Y Y.
!4r# component$ The antarafacial com'onent, )hich ma( have either . or B or 6- or Y Y
Y electron& of &ame t('e. The&e num+er& are o+tained +( &u+&tituting JrJ +( 6 or - or 1 or Y Y
Y.
<ike)i&e the meaning& of !4J B 2# & !4r#s can +e under&tood.
Appliction$
<et u& a&&ume the diene and dieno'hile in Fiel&9Alder reaction are a''roaching
&u'rafaciall( a& &ho)n +elo).
ince there are . electron& in diene, )hich i& making +ond& in &u'rafacial manner it i& a
!4J B 2#s com'onent@ i.e, there i& one /.E ; -0& com'onent.
And the alkene i& a !4r#s com'onent, &ince it ha& - electron& and i& a''roaching the
diene &u'arfaciall( i.e., there are no /.r0a com'onent&.
:ence, the total num+er of /.E ; -0& and /.r0a com'onent& = 6 ; 2 = 6, an odd num+er.
Therefore Fiel&9Alder reaction i& thermall( allo)ed in ground &tate )hen +oth the
com'onent& are a''roaching &u'rafaciall(. :ence it i& termed a& .& ; -& c(cloaddition.
Antarafacial addition, for thi& reaction, i& not allo)ed under thermal condition&. !ut it i&
theoreticall( allo)ed under 'hotochemical condition& in the e*cited &tate. :o)ever, the &train
in the tran&ition &tate )hile doing &o for+id& to do &o.
Note$ The or+ital& &ho)n in a+ove diagram& are &im'le J'J or+ital& and are not the frontier
molecular or+ital&. Fo not mi* de&cri'tion& of FM% theor( )ith Wood)ard9:offmann rule&.
(UCHEL0-"BIUS RULES BASE3 "N T"P"L"'7 "& AR"-ATIC
TRANSITI"N STATE
ince a''lication of a+ove Wood)ard9:offmann rule& to 'eric(clic reaction& i& tediou& and
cum+er&ome, the follo)ing &im'lified rule& +a&ed on aromatic tran&ition &tate 'ro'o&ed +(
Zimmerman can +e u&ed to 'redict theoreticall( allo)ed mode& of 'eric(clic reaction& under
given condition&.
The&e rule& are +a&ed on the conce't of to'olog( of aromatic tran&ition &tate. The c(clic
tran&ition &tate )ith 4nB2 electron& ha& :uckel to'olog( under thermal condition& and
Mo+iu& to'olog( under 'hotochemical condition&. :ence &u'ra facial interaction +et)een
or+ital& i& allo)ed under thermal condition&, )herea& antara facial interaction i& allo)ed under
'hotochemical condition&.
Wherea&, the c(clic tran&ition &tate )ith 4n electron& ha& Mo+iu& to'olog( under thermal
condition& and :uckel to'olog( under 'hotochemical condition&. :ence antara facial
interaction +et)een or+ital& i& allo)ed under thermal condition&, )herea& &u'ra facial
interaction i& allo)ed under 'hotochemical condition&.
No@ of electrons Rection con,itions
T:pe of Aromticit:
in
Trnsition stte
Allo5e, mo,e
/.n;-0
A :uckel num+er
Thermal :uckel u'ra /or0 Fi&
Ghotochemical Mo+iu& Antara /or0 Con
/.n0
A non :uckel num+er
Thermal Mo+iu& Antara /or0 Con
Ghotochemical :uckel u'ra /or0 Fi&
Memem+er that even though the 'eric(clic reaction& are allo)ed theoreticall( under +oth
the condition&, mo&t of the time& the factor& like &teric hindrance and &train in the tran&ition
&tate ma( for+id the reaction in 'articular mode, e&'eciall( the antara facial one.
The detailed u&age of the&e rule& and theoretical +a&e i& e*'lained in the later &ection&.