COORDINATION (With Reac. Mech) PPT Notes BY DR. Kuldeep Garg

COORDINATION CHEMISTRY
CLASS NOTES FOR CSIR-NET/GATE/IIT JAM/TIFR/BARC/GSI
By–Dr. KULDEEP GARG (KD SIR)
For more notes follow my telegram channel- kuldeepgargchemistry
Dr. Kuldeep Garg (KDSIR CLASS NOTES) 1

Coordination Chemistry Lecture – 1
Complete Coordination Chemistry

INTRODUCTION
Question 1. Ek compound A hai aur ek compound B hai …suppose CFSE of A is
1500 cm-1 and CFSE of B is 2000 cm-1. Which compound is more stable ?
a) A
b) B
c) Both are equally stable
d) Data is not sufficient
Dr. KULDEEP GARG
Answer – (d)
CFSE is a difference. Suppose hume btana hai ki sir ki pocket mei kitne paise hai
… door se dekh k idea lgaya ki Rs. 5000 honge … but after reasearch or checking
and only Rs. 600 mile … difference between 5000 and 600 is known as CFSE. 2
Dr. Kuldeep Garg (KDSIR CLASS NOTES)
CFSE ek type ka difference hai theoretical and experimental values ka aur
difference k basis pr stability nhi bta sakte hai
CFSE = Experimental – theoretical
Example – [Mn(H2O)6]2+ this compound is not unstable … kuki iski CFSE = 0 hai
isko unstable nhi keh denge …
CFSE = 0 ka matlab hai ki… Experimental – theoretical = 0
Question 2 – What is the hybridisation of [Re(CH3)6] and [W(CH3)6] ?

a) Both are same
b) Both are different
c) Both are sp3d2
d) None of these is sp3d2
Dr. KULDEEP GARG
Answer – (b) and (d)
hybridisation of [Re(CH3)6] = sd4p
hybridisation of [W(CH3)6] = sd5
Dono ki geometry = Triagonal prismatic

• When d0 and [M(CH3)6] = hybridisation will be sd5
• When d1 and [M(CH3)6] = hybridisation will be sd4p
Question 3 – inme se kon jyada stable hai …
A. [Mg(H2O)6]2+
B. [Ca(H2O)6]2+
C. [Sr(H2O)6]2+
Answer – (A) [Mg(H2O)6]2+

Yaha oxidation state nhi dekhna hai … hume metallic character dekhna h
Formal charge kitna hai … H2O ko negative ki tarah treat karenge … sab pr -4 ka
formal charge aaya … -4 charge ko kon rakhna pasand karega … koi metal hai …
jese jese metallic character increase hoga … minus charge rakhna pasand nhi
karega … aur positive hona pasand karega
Jitna jyada metallic character ; utna hate karega negative charge ko … metallic
character increases down the group
Stability is a relative phenomenon. Stability alag alag type ki hoti hai.

Sabse pehle hum thermodynamic stability dekhte hai …
• [Ni(CN)6] does not exist ; [Ni(CN)3] exist ; [Ni2(CN)6] exist

Hum common coordination = 6 milta hai … but we know less than 6 coordination
bhi exist krte h … jyada bhi milta h 6 se
❖ Electroneutrality principle
1) S block
2) P block
3) D block
4) F block
Sab pr Electroneutrality principle lagta hai … lekin ku nhi padhte … kuki
applications hrr block k liye different hai …
Thermodynamic stability is not applied on d block
Baaki sab pr lg jaata h
Question 4 – order of stability of
1. [Fe(H2O)6]2+
2. [Ru(H2O)6]2+
3. [Os(H2O)6]2+
Answer - [Fe(H2O)6]2+ < [Ru(H2O)6]2+ < [Os(H2O)6]2+
Yaha oolta ho gya order … p block wale se … iss liye confuse nhi hoga
❖ d block mei thermodynamic stability formal charge k basis pr nhi dekhni h
Question – what is the formal charge on [Ni(CO)4] and [Ni(Cl)6]2- ?

Answer - formal charge on [Ni(CO)4] = 0
formal charge on [Ni(Cl)6]2- = +2 … wrong hai … +2 is oxidation state
formal charge on [Ni(Cl)6]2- = 0
Ye hum prove karenge by electroneutrality principle
❖ Oxidation state increases as coordination number increases … ye hum padhte hai
o [Na(H2O)6]+
o [Mg(H2O)6]2+ as oxidation charge increases; coordination number is same
o [Al(H2O)6]3+
In p block ; as oxidation state increases ; coordination number increases
o SF4
o SF6
In lanthanides ;
▪ Ce+2 Lx
▪ Ce+4 Ly
Here x > y; +4 oxidation state mei bhi coordination number less hai
❖ High O.S. (oxidation state) ; higher stabilty … aisa nhi hai
❖ [Ni(CO)4] ; O.S. = 0 ; rone lga
❖ [V(CO)6]- ; metal pr negative charge …haye haye macha deta …
Mo ki -4 O.S. tk jaata hai

Question – NO3- is
a) Monodentate
b) Bidentate
c) Flexidentate
d) None of these
Answer – (C)
Behave as monodentate with 3d metals
3 membered chelate rings are unstable
4 membered chelate rings are stable but condition hai ki metals ka size big ho
Jb NO3- lanthanides k saath judte h toh do side se donate krte h
• For 3d metals – 5 > 6 > 4 > 3 membered ring

• For lanthanides 5 > 4 > 6 > 3membered ring
• acac - acetoacetate – iske saath metal 6 membered ring banata hai

Ye sigma donor bhi hota hai and pi donor bhi hota hai … resonance bhi ho rha hota
h … aromatic character aa jata hai that’s why 6 membered ring stable ho jaati h

Question – [Mg(EDTA)H2] mei kitna coordination number hoga … aisa pooch lete
h
Question - NH2-NH2 is a
a) Monodentate
b) Bidentate
c) Flexidentate
Answer – (a) monodentate
3 membered ring kabhi nhi banegi … humesha monodentate hi rahega …
Ab sab doubts finish … ab padhna start karenge

COORDINATION CHEMISTRY
Sabse pehle toh coordination hai kya
Isko hum samjhenge salt se … ek hota h normal salt … ghar ka namak … NaCl
Thode se addition compounds bhi hote h jo ki 2 type k hote h
1. Double salt
2. Complex salt
NaCl ne apne pyaar ka test diya …Isko paani mei daal dete h … aur inka pyaar toot
jaata h
• NaCl + H2O → Na+ + Cl- … no identity of NaCl in aqueous solution
Aise hi double salt k saath hua
• KCl.MgCl2 + H2O → K+ + Mg2+ + Cl-… no identity of KCl.MgCl2 in aqueous
solution
• Ions ki identity retain kiya but salt ki identity lose ho gyi
• K4[Fe(CN)6] + H2O → K+ + [Fe(CN)6]4- … [Fe(CN)6]4- retained its identity in
the aqueous solution
• Solution mei iron k ions nhi mile … cyanide k ions nhi mile … ab hume ye
dekhna hai ki [Fe(CN)6]4- ye kaise jude rahe … inka relation pta krne mei lge
K4[Fe(CN)6] is known as complex compound
METAL – LIGAND k complex ko COORDINATION COMPLEX bola
Alag alag theory aane lgi inke relation batane k liye … lovers nhi hai … kuki water
daalte hi alag ho jate … lovers means ionic bond is not there
Pauling gave a theory … theories hai … concept nhi hai …

VBT theory aayi … kehne lgi ki metal k d orbitals khaali the usme electron donate
krne laga ligand … metal donates electron ; ligand donates electron toh electrons
jaa kaha rhe hai jb dono donate kr rhe h toh … explained on the basis of
electroneutrality principle
Hydrogen k paas kitne orbitals hote h ?

Ans. Infinite orbitals
H k orbitals mei de dete electron … usko ku nhi diye

Jb metal apne electrons donate krke aa jaata hai … tb ligands ko kehta h ki hum
dono ek doosre k electrons ko neutralise krenge … ek ligand lga hua h … lekin koi
doosra ligand aaya toh pehle wale ko bhaga k new ko lga le

We will study this in detail
Why werner got the Nobel prize ?
Why carbonyl give metal to metal but accepts electron ?

Coordination Chemistry Lecture – 2(16)
WERNER THEORY
Werner got a nobel prize in coordination chemistry
Werner ko nobel prize ku mila … [XY] compound liya ; geometry define kr di
without spectroscopy
[ML6] can have following geometries
Hexagonal planar Trigonal prismatic Octahedral

Werner gave [ML6] geometry → octahedral on the basis of isomerism.
Jab geometry pta lag gyi ; uske baad bonding nature determine kiya gaya
By VBT ; CFT ; LFT
Molecular formula – Cr(NH3)6Cl3

▪ [Cr(NH3)6].3Cl
▪ [Cr(NH3)5Cl].2Cl
▪ [Cr(NH3)4Cl2].Cl
Dr. KULDEEP GARG
▪ [Cr(NH3)3Cl3]
Werner ne experiment kiya, water mei daal diye ; jo water daalne se alag ho gye
unhe bracket k bahar rkha aur jo alag nhi hue unke beech bond bnaye

Physical and Chemical properties should be different for all
But werner got only two types of properties of the above compound instead of 3.
So he thought of another geometry

Still hume 3 type ki properties mili ; koi or geometry sochi

2 type ki properties mili ; we got two types of compounds.
Therefore, the compound has an octahedral geometry
POSTULATES OF WERNER THEORY

Valency 2 type ki hoti hai
1. Primary valency
2. Secondary valency
Primary valency → Oxidation state of central metal atom

Secondary valency → Coordination of central metal atom
Primary valency is ionizable, whereas secondary valency is non-ionizable

H2O
[Co (NH3)6]3+Cl3 [Co (NH3)6]3+ + 3 Cl-
Primary Valency can be satisfied only by negative ion

[Co (NH3)4Cl2]+Cl
2 Cl- is satisfying primary valency
• Secondary valency can be satisfied only by negative or neutral ion
• Primary valency is non directional
• Secondary valency is directional
Primary valency → O.S. → Ionizable → negative → non-directional
Secondary valency → C.N. → non-ionisable → negative / neutral → directional

[M (NH3)4Cl2]Cl
[M (NH3)5Cl]Cl2
[M (NH3)6]Cl3
Physical properties were checked :-
1. Electrical conductivity
2. Depression in the freezing point (DFP)
Charge ↑ , Electrical conductivity ↑
Number of charged particles ↑ , DFP ↑
conductivity
a) [M (NH3)4Cl2]Cl → |+1-1| = 2 particles
b) [M (NH3)5Cl]Cl2 → |+2-2| = 3 particles
c) [M (NH3)6]Cl3→ |+3-3| = 4 particles
a b c
Chemical reaction
[M (NH3)4Cl2]Cl + AgNO3 → AgCl
[M (NH3)5Cl]Cl2 + AgNO3 → 2 AgCl Proved by werner
[M (NH3)6]Cl3 + AgNO3 → 3 AgCl
Bonding nature of M-L bond Dr. KULDEEP GARG

Isko hum VBT, CFT , LFT se explain karenge
Isse pehle kuch basic seekh lete hai
• 18 electron rule
• Electroneutrality principle

18 electron rule bhi octet rule k jaisa hi hai … isko hum stabibility dekhne k liye
use krte hai
Agar compound 18 electron rule ko follow karta hai, iska matlab hai ki voh
compound stable hai
Agar koi compound 18 electron rule ko follow nahi karta hai toh iska ye matlab
bilkul nahi hai ki voh compound unstable hai
ELECTRONEUTRALITY PRINCIPLE
Ye um 2 jagah padhte hai
➢ Transition metals mei (d1 – d9)
➢ Non transition metals mei (s-block, p-block, lanthanides and actinides, d0 and
d10)

Pehle hum padhte hai ELECTRONEUTRALITY PRINCIPLE FOR TRANSITION
METAL CHEMISTRY
We know, Oxidation state increase ; stability increase

But THIS IS NOT STUDIED IN TRANSITION METAL CHEMISTRY
Kuki transition metal chemistry mei aise compounds bhi hai jinka oxidation state
less hai but voh stable hai
For example, [V(CO)6]- → Low oxidation state mei hai metal ; but this compound
is stable
[Fe(CN)6]3- → high oxidation state mei hai metal ; this compound is stable
Oxidation state increase ; stability increase → ye hum p – block mei apply krenge

AlF63- ; SF6 ; PF6- ; SiF62-
Al3+ < Si4+ < P5+ < S6+ increasing order of oxidation state
Order of stability - AlF63- <SiF62- < PF6- <SF6
Ligand k basis pr stability nahi bata sakte

AlF63- ; Al(H2O)63+ ; Al(H2O)63+
All have Al3+
F is more electronegative – electron ache se kheech k rakhega ; aur Al pr 𝛿 +
charge badha dega ; jitna jyada charge ; utni jyada stability .
Charge pr based stability only p – block mei bata sakte hai

When ligand and charge is same – we can tell stability only in transition metals
Summary for non transition metals

• Ligand same → O.S. different → O.S. ↑ , Stability ↑
• Ligand different → O.S. ya charge same → most electronegative atom ligand
increases ; 𝛿 + charge badha diya aur stable kr diya
• Ligand same ; charge same → formal charge dekhenge
formal charge induce kiya ; aur dekha 𝛿 − ko kon rakh sakta hai . Iss liye kam
metallic character wale ne 𝛿 − ko rakh liya aur stable ho gya ; therefore
[Mg(H2O)6]2+ is more stable (refer first lecture)
THIS STABILITY IS THERMODYNAMIC STABILITY

Charge k basis pr , transition metal complexes mei thermodynamic stability nahi
dekhenge
On the basis of Charge
We can see coordination number ; only in transition metals
We cannot see coorn=dination number in non transition metals on the basis of
charge
❖ s – block
o [Na(H2O)6]+
o [Mg(H2O)6]2+ as oxidation charge increases; coordination number is same
o [Al(H2O)6]3+

❖ p – block
SF4 → +4
SF6 → +6 charge increase ; coordination number increases
❖ Lanthanoids
Ce2+ → C.No. = 12
Ce4+ → C.No. = 6 charge increase ; coordination number decreases
❖ Transition metals
CHARGE INCREASE ; COORDINATION NUMBER INCREASES

❑ [NiCl4]2- and [NiCl6]2-
Ni2+ mei coordination number = 4 hai ; jaise hi Ni4+ hua means oxidation increase
hua ; coordination number bhi 6 ho gya ; that means increase ho gya
[NiF6]2-
Electronegative atom lagane se bhi charge increase hota hai … F is more
electronegative ; electron apne paas rakhe ; metal pr 𝛿 + charge increase ho gya
Therefore, as charge increase; coordination number increases
❑ [Cu(NH3)4] and [CuF6]4-

N is less electronegative than F ; F is more electronegative ; electron apne paas
rakhe ; metal pr 𝛿 + charge increase ho gya

❑ [CoF6]4- ; [Co(NH3)4]2+ ; [Co(NH3)6]3+
[CoF6]4- ; [Co(NH3)4]2+ here electronegativity increase hui ; charge increase hua;
coordination number increase ho gya
[Co(NH3)6]3+ - yaha toh charge hi increase ho gya ; +2 se +3 ho gya ; coordination
number increase hoga hi
Coordination number depends upon –

• Charge
• Number of d-electrons Dr. KULDEEP GARG
• Number of d-electrons ↑ coordination number ↓
• charge↑ coordination number ↑
(due to electroneutrality principle)
d1 se d10 ki taraf jaate hue … Co tak toh humne coordination number 6 k complexes
milte hai … after Co we get complexes with coordination number 4
Aisa ku hua ?
Metal k d electron increase ho rhe hai … toh ligand k electron rakhne k liye space
nhi hai … iss liye ligand hi kum kr diye
If Co k baad wale metals ka coordination number increase krna hai … iske liye 2
methods hai
1. Oxidation state increase kr do
2. Ligand ko highly electronegative kr do
[Cu (H2O)6] and [Ni (H2O)6] exist because Oxygen is electronegative.

K2[[Ni Cl6] ; here nickel is in +4 oxidation state ; O.S. increase hua ; coordination
number bhi increase ho gya ; that is 6
Ab tk humne dekha ki electroneutrality k according

• Metal k liye 2 points hai
➢ Oxidation state should be high
➢ Coordination number should be high
• Ligand mei bhi hum 2 cheeze dekhenge

➢ Sigma bond – electronegativity
➢ Pi-bond – back bonding
(inko aage detail mei explain karenge)
Ligands are classified on the basis of donation

1. Classical (electron donate karega)
2. Non-classical (electron donate bhi karega aur accept bhi karega)
Classical – jo apna kaam ek dm perfectly kare

Ligand ki definition – that donate electrons are known as ligands
Ek term humne suni hoti hai … COORDINATE BOND

Ye bhi 2 type ka hota h
➢ Sigma coordinate bond
➢ Pi coordinate bond
Suppose 3 people - A , B and C temple mei gye
A (Kuldeep sir ) ne toh 10 rupees ka prashad chadhaya … aur badle mei bohat saari
wishes maang li
B (kuldeep sir ki wife ) ne 10 rupees ka prashad chadhaya … saath mei paise bhi
diye
C (kuldeep sir ka son) ne sirf 10 rupees ka prashad chadhaya
M L A = σ – donor + π – acceptor { NON – CLASSICAL}
M L B = σ – donor + π – donor { CLASSICAL}
M L C = σ – donor { CLASSICAL}
All ligands are σ – donors
σ – bond stabilization is dependent on electronegativity of ligand
• Blue arrows jo bond show kiye gye hai voh hai σ – coordinate bond (also
known as DATIVE BOND )
• Red arrows show π – coordinate bond
• NH3 → BH3 (Dative bond)
Question – Which statement is correct?

A. All coordinate bonds are dative bonds
B. All dative bonds are coordinate bonds
Answer – B
Spectrochemical series
σ – donor + π – acceptor > only σ – donor > σ – donor + weak π – donor
> σ – donor + strong π – donor
red bond is π – back bond also called synergic bonding
red bond shows π – back bonding
➢ If metal is in high oxidation state, kon se ligand se bonding karega ?

Electron kum hai ; jo electron de dega ; σ – donor toh sab hai ; therefore π – donor
ligand se bonding karega
e.g. KMnO4 Mn+7 → O is a σ – donor and weak π – donor
➢ If metal is in low oxidation state, kon se ligand se bonding karega ?
Electron jyada hai ; jo electron le lega ; therefore π – acceptor ligand se bonding
karega
e.g. [V (CO)6]- V- → CO is a σ – donor and π – acceptor
Mo-4 with CO → highly π – acceptor
❖ CO is ambident or not ? M ← CO ; Answer is No

❖ CN is ambident or not ? M ← CN ; Answer is No
❖ SCN is ambident or not ? YES ; M ← SCN ; M ← NCS
❖ Gap is high in C and N

❖ Gap is low in N and S

[Ni Cl4]2- Ni2+ → O.S. = +2 ; formal charge = 0
Chlorine is more electronegative ; electron chlorine k paas hi rahenge
❑ M C=O
Jab CO ko electron wapas hi lene the toh diye hi ku ?
C and O ne bond banaya, 2 valency thi dono

ki, satisfy ho gyi but C had 2 non bonding
electrons, Oxygen is more electronegative
than Carbon; therefore, oxygen is placed at
lower energy level

Carbon was not happy because uske electrons non bonding with slightly
antibonding character mei the … Therefore, tries to donate to Mn+ ; Mn+ ko
electrons chahiye but does antibonding k nahi chahiye ; fir Carbon ne kaha ki ek
baar le le fir mujhe wapas de dena and Carbon fir accept karta hai metal se
electrons ko in π* of CO
Firstly, electrons the nb(ab) of carbon mei ; ab electron hai π* of CO
M-C=O
In carbonyl chemistry, jitna acha M → π bond (back bond) banayega ; utna C=O
bond weak hoga kuki metal electron dega anti bonding of CO mei ; bond order of
CO decreases

VALENCE BOND THEORY
This theory was given by Pauling
Metal k paas degenerate orbitals of comparable energy hai
Comparable means → 100, 110, 130 – mila lenge
1, 1000000 – ye comparable nahi hai
• Metal k paas vacant orbitals of comparable energy hote hai ; that can accept
electrons from ligands
• Ab ye dekhte hai ki konse orbitals comparable energy k hote hai
❖ 3d ; 4s ; 4p and 4s ; 4p and 4d
3d and 4d apas mei hybridise nahi kr sakte hai ; l value same ; n value different

Metal k d ; s ; p orbitals hybridise hoke M-L complex banayenge
say, kuch guests aa rhe hai papa ki side k ; mamma will ask kitne log aa rhe hai ;
agar 3 log aa rhe honge sitting arrangement is according to 3 guests
We know, geometry toh fixed hai ; iske according hum hybridisation de denge
Suppose, geometry hai octahedral

Hybridisation humne maan li d2sp3 or sp3d2
s is non directional
p is direction
d is diffused
Isme jo 2 d oribitals use ho rhe hai voh hai d x2-y2

In octahedral, dxy ; dyz and dzx will not hybridise with d x2-y2 and d z2
Because angle is very less than 900
sd5 – ye octahedral nahi hai ; Dr. KULDEEP GARG

Kuki hume pata hai ki octahedral mei saare angles 900 and 1800 hi hote hai
And all 5 d orbitals are not at 900
Therefore; octahedral geometry banane k liye hum ya toh d3 ( dxy; dyz; dzx) use kr
sakte hai ya fir d2 (d x2-y2 and d z2)
Agar hum d3 ( dxy; dyz; dzx) use krte hai – d3sp2

dxy and px orbitals 900 pr nahi honge
dxy and pz mei toh 900 ka angle ka hoga ….
Lekin px and py k saath nahi hoga
Ya toh px and py bhi dxy se overlap ho jaate

Agar nhi hue toh 900 pr rahe
Therefore; d3sp2 is also not good for octahedral.

ALL p orbitals overlap with d x2-y2 and d z2
Iss liye d2sp3 or sp3d2 are suitable for octahedral geometry

Coordination Chemistry Lecture – 4 (18)
VBT - isme hum metal k hybrid orbitals consider karte hai jinki energy jo hai voh
comparable hai ; metal ligands k saath covalent coordinate bond banata hai
According to VBT, ligand is of two types

Life mei 2 types k people hote hai
Rich and poor
But ye nahi bata sakte ki konsa rich konsa poor ; we will see spin only magnetic
momenta
Two types of ligand – check karenge sabse pehle magnetic momenta
Agar electron ka spin only magnetic momenta k hisaab se agar electron Hund’s rule
ko follow karta hai ya hund’s k jaisa nahi hai … ye check krenge
• If number of unpaired electron in metal = number of unpaired electron in
complex ; Then the LIGAND IS WEAK
• If number of unpaired electron in metal > number of unpaired electron in
complex . Then the LIGAND IS STRONG
• Strong ligands have tendency to pair up the electrons to stablise the complex. If
complex gets destablised – pairing will not occur.
• Weak ligands do not have tendency to pair up electron.

Octahedral – d2sp3
3d k 2 orbitals 4s orbital and 4p orbital ye sab mil jaate hai ; hybridise kr lete
Jab 3d available na ho, tabhi 4d ko include karenge
Agar 4d ko involve karenge toh uski hybridisation hogi sp3d2
• Agar andar wale d orbitals participate kr rhe hai ; that means 3d involve hai;
d2sp3 (d andar likha hai) this is known as OUTER ORBITAL COMPLEX
• Agar bahar wale d orbitals participate kr rhe hai ; that means 4d involve hai;
sp3d2 (d bahar likha hai) this is known as INNER ORBITAL COMPLEX
Strong ligand will not pair because easily d2sp3 is available
This is very unstable . Kinetically unstable.

This man can bear 600 Temperature; but haath pair toot gya hai; no samajhdaari
Hybrid orbital ki energy ka hi orbital khaali pada hai
Jagah khaali dikhi … water aake beth jayega…aur baaki ligands ko bhi replace
karna shuru kr dega
Hybrid orbital ki energy ka orbital vacant hai toh LABILE ; otherwise INERT
➢ On the basis of kinetic stability, compounds can be of two types

❖ Labile
❖ Inert

d1 and d2 are labile
d3 is inert
Dr. KULDEEP GARG
d1, d2 and d3 are inner orbital complexes
d1, d2 and d3 pr strong aur weak ligand ka koi effect nhi hoga
d4 metal
Due to this vacant orbital of low energy → Highly Labile

Hybridisation is sp3d2 and complex is outer orbital complex
Hybridisation is d2sp3 and complex is inner orbital complex and inert.

Agar iss tarah se pairing karvayenge ; ye labile hai ; kinetically unstable hai
KINETIC AND THERMODYNAMIC STABILITY

• A-B ka bond todna hai … easily toot rha h hathoda maarne pr lekin 100 saal
mei toot raha hai . Therefore, KINETICALLY STABLE
• A-B compound banaya; 100 KJ/mol ki energy mei bann gya easily lekin raha
sirf 1 minute ; therefore, KINETICALLY UNSTABLE
• There is no relation between thermodynamic and kinetic stability

Similarly hum sabka bana sakte hai

All square planar geometry are permanently labile because of its geometry
Upar se attack easily ho sakta hai metal par
d7 – no effect here ;
d8 – strong / weak – OSC → sp3d2 → Labile
d9 – strong / weak – OSC → sp3d2 → Labile

Low coordination number
Which one will make coordination number = 1 , 2 , 3
1 → Cu+, Ag+, Au+
2 → Cu+, Ag+, Au+ , Hg2+
3 → Cu+, Ag+, Au+ , Hg2+ , Ni2+, Pt0

d1 Weak/strong d2sp3 I.O.C. Labile Paramagnetic
d2 Weak/strong d2sp3 I.O.C. Labile Paramagnetic
d3 Weak/strong d2sp3 I.O.C. Inert Paramagnetic
d4 weak sp3d2 O.O.C. Highly labile Paramagnetic
Strong d2sp3 I.O.C. Inert Paramagnetic
d5 Weak sp3d2 O.O.C. Labile Paramagnetic
Strong d2sp3 I.O.C. Inert Paramagnetic
d6 Weak sp3d2 O.O.C. Labile Paramagnetic
strong d2sp3 I.O.C. Inert Diamagnetic
d7 Weak/strong sp3d2 O.O.C. Labile Paramagnetic
d8 Weak/strong sp3d2 O.O.C. Labile Paramagnetic
d9 Weak/strong sp3d2 O.O.C. Labile
Dr. Kuldeep Garg (KDSIR CLASS NOTES)
Paramagnetic 57
❑ 4d and 5d metals → always pairing (weak or strong)
❑ Strong and weak sirf 3d (d4, d5, d6) upto +3 oxidation state
❑ Note : metal having O.S. ≥ +4, always pairing
Question.(GATE 2015) K2NiF6 ka hybridisation kya hoga?

Answer. NiF62-
Ni → x – 6 = -2
x = 6 – 2 = +4
Ni+4 →d6 (+4 O.S. → pairing hogi)
Answer – d2sp3
Ligands - C N O Halogen
C-O N-O
C-N
N, C apne se jyada electronegative atom se jude ho – strong ligand
O k baad weak ligands, Halogens – weak ligand
CO, CN, NO, NO2 > NH3, en > H2O, OH > F, Cl, Br, I
STRONG MODERATE WEAK VERY WEAK
This is a rough idea
• NH3, en behave as strong ligand in O.S. +3 and above otherwise weak
• With Co3+ , H2O, OH (O ki side se donation) ; behave as strong

Magnetic momenta = 𝑛 𝑛 + 2 B.M = 4𝑆(𝑆 + 1) B.M.
Number of unpaired electron BM

1 1.7
2 2.8
3 3.9
4 4.9
5 5.9
QUESTION. For the given complexes list the following

1. Hybridisation
2. Labile/inert
3. Paramagnetic/diamagnetic
4. Magnetic momenta
5. OOC/ IOC
I. [Fe(CN)6]4-
Fe → x – 6 = -4
x = 6 – 4 = +2
Fe+2 →d6
CN is a strong ligand ; pairing hogi
1. Hybridisation = d2sp3
2. inert
3. diamagnetic
4. Magnetic momenta = 𝑛 𝑛 + 2 B.M= 0 0 + 2 B.M =0 B.M
5. IOC
II. [Fe(NH3)6]2+
Fe → x – 0 = +2
x = +2
Fe+2 →d6
NH3 is a weak ligand ; pairing nhi hogi
1. Hybridisation = sp3d2
2. labile
3. Paramagnetic
Dr. KULDEEP GARG
4. Magnetic momenta = 𝑛 𝑛 + 2 B.M= 4 4 + 2 B.M =4.9 B.M
5. OOC
III. [Os(H2O)6]2+
Os → x – 0 = +2
x = +2
Os+2 →d6
4d series; pairing hogi
2. inert
3. diamagnetic
4. Magnetic momenta = 𝑛 𝑛 + 2 B.M= 0 0 + 2 B.M = 0 B.M
5. IOC

IV. [Co(H2O)6]3+
Co → x – 0 = +3
x = +3
Co+3 →d6
Dr. KULDEEP GARG
H2O is strong with ; pairing hogi
2. inert
3. diamagnetic
5. IOC

V. [Cr(H2O)6]2+
Cr → x – 0 = +2
x = +2
Cr+2 →d4
H2O is weak ; pairing nahi hogi
2. labile
3. paramagnetic
4. Magnetic momenta = 𝑛 𝑛 + 2 B.M= 4 4 + 2 B.M = 4.9 B.M
5. OOC

VI. [Cr(NH3)6]2+
Cr → x – 0 = +2
x = +2
Cr+2 →d4
NH3 is weak ; pairing nahi hogi
2. labile
3. paramagnetic
5. OOC

VII. [IrF6]3-
Ir → x – 6 = -3
x = +3
Ir+3 →d6
5d series; pairing hogi
2. inert
3. diamagnetic
5. IOC

Question (GATE)-
[Fe(NH3)6]2+→ Fe2+ →NH3 (weak ligand)
[Fe(NH3)6]3+→ Fe3+ →NH3 (strong ligand)
Question
[Co(NH3)6]2+→ Co2+ →NH3 (weak ligand)
[Co(NH3)6]3+→ Co3+ →NH3 (strong ligand)
Question
[Os(NH3)6]2+→ Os2+ →NH3 (always pairing ; 5d metal hai)

GATE (2015) – hybridisation of K2[Ni F6]
If hybridisation is asked – answer according to VBT
[Ni F6]- → Ni4+ →d6→d2sp3
NO2 can do transfer of electron

Iska sirf ek hi example hai … [Co(NO2)6]4- → Co2+ →d7

Air mei oxidise hua ? Kyu hua ?
Explaination – ek electron very high energy state mei excited hai … iss liye oxidise
ho gya ; one electron is in 5s orbital
Energy ka order – 3s < 3p < 4s < 3d < 4p < 5s < 4d
4s and 5d can not be used in hybridisation

But jab hume kisi electron ko excite karana hota hai ; it will be excited in 5s ;
because 4p is involved in hybridisation
[Co(NO2)6]4- → d2sp3 but labile hai

Question. I. [Ir (H2O)6]3+ ; II. [Cr(NH3)6]2+ ; III. [Ni (H2O)6]2+ ; IV. [Os F6]2-
(a) d2sp3 and paramagnetic
(b) sp3d2 and diamagnetic
(c) d2sp3 and diamagnetic
(d) sp3d2 and paramagnetic
Answer
I. [Ir (H2O)6]3+
Ir → x – 0 = +3
x = +3 ; Ir+3 →d6 ; 5d series; pairing hogi
2. Diamagnetic
II. [Cr(NH3)6]2+
Cr → x – 0 = +2
x = +2 ; Cr+2 →d4 ; NH3 is weak ligand; pairing nahi hogi
2. paramagnetic
III. [Ni (H2O)6]2+

Ni → x – 0 = +2
x = +2 ; Ni+2 →d8 ;
2. paramagnetic
IV. [Os F6]2-
Os → x – 6 = -2
x = +4 ; Os+4 →d6 ; 5d series; pairing hogi
2. Diamagnetic
Question. Correct option for [Fe(H2O)5 NO]2+

a. Unpaired electron = 4 ; labile; sp3d2
b. Unpaired electron = 3 ; labile; sp3d2
c. Unpaired electron = 2 ; inert; sp3d2
d. Unpaired electron = 1 ; inert; sp3d2
e. Unpaired electron = 4 ; inert; d2sp3
Solution. NO+ (learn)
Fe → x + 1 = +2
x = +1 ;
Fe+1 → 3d6 4s1 ;
sd pairing – s orbital is involved in hybridisation 100%
Ligand ka nature kuch bhi ho ; s k electron d mei pair honge ; d-d pairing nahi hogi
kuki weak ligand hai

Only 3 unpaired electron – magnetic moment = 3.9
[Fe(H2O)5 NO]2+ gives brown ring test
[Ni (CO)4]
Ni→ x = 0
Ni0 → 3d8 4s2 → d10 converted compound

[Co (CO)4]- and [Fe (CO)4]2-
Both show s-d pairing – dono converted d10 systems hai
[Co (CO)4]-
Co→ x = -1
Co-1 → 3d8 4s2 → d10 converted compound
[Fe (CO)4]2-
Fe→ x = -2
Fe-2 → 3d8 4s2 → d10 converted compound
ALL THE THREE COMPLEXES ARE sp3

COORDINATION NUMBER = 4
Yaha 2 types ki geometry dekhne ko milti hai

1. TETRAHEDRAL
2. SQUARE PLANAR
Tetrahedral jab hoga toh 2 hybridisation possible hai

➢ sp3 and d3s
Square planar jab hoga toh 2 hybridisation possible hai

➢ sp2d and dsp2

➢ [Ni (CO)4]
Ni→ x = 0
Ni0 → 3d8 4s2 → d10 converted compound → sp3
➢ MnO4-
Mn→ x - 8 = -1; x = +7
Mn+7 → 3d0 → d3s (isme jo 3 d orbitals involved hai ; voh hai dxy, dyz, dzx, s)
Exception - MnO4- is paramagnetic ; we will study in magnetism

Paramagnetism 2 wajah se hota hai ; spin and orbital
Spin wale ko kehte hai – temperature dependent paramagnetism
Orbital wale ko kehte hai temperature independent paramagnetism
MnO4- show orbital paramagnetism (temperature independent paramagnetism)
And spin k basis pr pooche toh temperature dependent diamagnetic
[Cu (NH3)4]2+
Cu+2 → 3d9
VBT k according sp3 hona chahiye ; lekin jab spectroscopy develop hui ;
compound ka ESR kiya ; geometry square planar mile ; for square planar all 3p
orbitals are never used; kuki px , py and px kabhi bhi ek hi plane mei nahi aa sakte

Kuch logo ne kaha ki ek electron ko 5s mei daal do aur dsp2 mil jayega
Huggin’s ne kaha ki electron bahar hai toh oxidise hona chahiye easily
Air mei le jao ; Cu3+ milega; nhi mila
H2O2 daal do ; electron bahar aa jayega … nahi aaya
Huggin’s concept – kisi bhi electron ko aise hi utha k bahar nhi rakh skte

sp2d ko JTD se explain kiya gya ; [Cu (NH3)4]2+ direct bn hi nhi rha
Cu + NH3 → [Cu (NH3)6]2+ {ye ek d9 complex hai ; high JTD hogi isme}
[Cu (NH3)6]2+ is a Zout complex; iski age bohat kum hai
sp2d – (px and py and dx2-y2) ; dz2 and pz wale bhaag jate hai

DRAWBACKS OF VBT – (SYLLABUS OF CFT)
1. It could not explain pairing
• 4d-5d pair kr rhe hai
• Nature of ligand
• +4 se jyada wale pair
Ye sab kaise ho rha hai ; no explaination
2. VBT could not explain the different bond lengths

2 bonds chote ; 4 bond lambe ; usne sab bonds ko same maana
Therefore, bond energy ka difference aaya ; not defined
3. VBT says colour is due to transition ; d-d transition nhi pta tha isse kuki all d
were at same energy Dr. Kuldeep Garg (KDSIR CLASS NOTES) 82
VBT ne 3d se 4d mei transfer kiya – ye transition visible range se bahar jayega ; it
does not explain spectra
4. Could not explain magnetism. He considered only spin only momenta whereas
there is orbital momenta also which is temperature independent. Magnetic
susceptibility was not explained which is temperature independent.

CRYSTAL FIELD THEORY

• Given by Ban Bathe Black
• M-L → metal ligand bond is purely electrostatic interaction
• He has SOLID STATE PHYSICS is used
• Usne solid state considered M-L do not overlap
• Ionic – strong forces
• Electrostatic – weak forces
• SUPRAMOLECULAR CHEMISTRY – chemistry beyond the molecules (weak

interactions)
• Electrostatic interaction – strongest among weak forces
HOST – GUEST CHEMISTRY and DNA – RNA – self assembly
this dipole will also interact with Mn+
ELECTROSTATIC INTERACTION
Electrostatic interaction is of 2 types
Why are we studying splitting in d – orbitals ?

Ghar mei bethe hai … bahar se koi aadmi aaya fridge mei se paani peene laga …
azeeb laga but ignore kiya thoda bohat kuch keh diya … next day fir se aaya …
100 rupees lene laga … ek chaanta maara, note wapas liya aur bhaaga diya
Next day fir se aaya … saara saaman bahar fek rha hai … dande se maar diya usko
… bahar k logo ko reason nhi pata bss ye pta hai maar lg rhi h kuch bada panga
hua hai …
M+ and d – electrons have interaction.
L- ka bhi interaction hone lga … hume nhi pta
kitna interaction hai … but ye andaaza lagaya ki
jitni ladai d – electrons and L- ki hai utna jyada
interaction M – L ka hoga
Suppose 5 people hai ; unme se 2 ki ladai ho gyi

Aur baaki 3 khush ho gye ki M+ se maze karenge

in dono ka gap UV spectroscopy se measure ho jayega
kuki UV mei valence shell k electron ki saari information mil
jaati hai
Jitna jyada difference; utna jyada Mn+ L- ka interaction

• Koi door se jaa rha hoga ; toh usse ladenge nahi … paas aake dhaka maarega
tabhi ladai hogi … similarly, when Ligand comes nearer then only d electrons
start repelling it and utni jyada splitting hogi
• Electrostatic interactions are of two types

1. Primary interaction (attraction)
2. Secondary interaction (repulsion)
➢ PRIMARY INTERACTION - This is between Metal and ligand

➢ SECONDARY INTERACTION – This is of two types
a) Between d electrons and ligands
b) Between ligand and ligand (this will define the thermodynamic stability)
Jitna M- L paas aayega ; utna jyada d electron and ligand ka repulsion hoga
Also ligand – ligand mei aapas ka repulsion jyada hoga

3 geometries are studied in CFT
1. Tetrahedral
2. Octahedral experimental
3. Cubic
➢ Square pyramidal
➢ Trigonal bipyramidal hypothetical
➢ Pentagonal bipyramidal
❖ Square planar ise defined by JTD

❖ We are studying in SOLID STATE that’s why the name is crystal field theory
and crystal mei electrostatic field generate karvaya hai
Crystals → metal oxides because application mei spinal padhte hai
Spinals are metal oxides AB2O → found in ccp or fcc
Octahedral geometry chahiye toh ligand ka attack

face center se best hoga ; when metal is in the
center of cube
❑ ORBITALS (2 type k hote hai)

• d orbitals are six in number and are of two types
1. Along the axis – dx2-y2 , dz2-x2 , dz2-y2 (dz2 is a linear combinition of these
two)
2. Between the axis – dxy, dyz, dzx
ALONG THE AXIS – 6 leaves at face centers
Dr. KULDEEP GARG

BETWEEN THE AXIS – 12 leaves at edge center

Between the axis wale lie at edge center
Along the axis wale lie at face center
• Ligands are attacking at face centers

Jab d orbitals ko pta chala ki ligand aa rha hai, toh sab excited ho gye, ligandne kha
ki mae face center se aaunga … toh face center wale orbitals dx2-y2 and dz2 excite
ho gye aur edge center wale stable ho gye aur energy kum ho gyi
Splitting is called CRYSTAL FIELD SPLITTING (CFS)
• Repulsion between dx2-y2 and dz2 is increased and repulsion between dxy, dyz
and dzx is decreased
• Upar wale k paas 60 apne the ;

• 40 neeche walo se maang liye
• Energy conserved rakhni hai
• Neeche wale ne 40 de diye upar
wale ko

TETRAHEDRAL
For tetrahedral geometry, ligand will approach from
1. Alternate edge center (wrong)
𝜃 ≠ 𝛼 ;𝑎 ≠ 𝑏
From alternate edge center, we get distorted tetrahedral
2. Ligand will approach from ALTERNATE CORNERS

Regular tetrahedral milega
Direct attack nhi ho paaya… toh ligand jiske jyada
paas se gya uska thoda jyada repulsion

Ligand ka distance (ligand is at alternate corner)
➢ From alternate edge is a/2
➢ From face center is 2 𝑎/2
a/2 is less ; therefore, ligand will approach from nearby between the axis

CUBIC
For cubic geometry, ligand will approach from all the corners
Similar to tetrahedral, between the axis wale paas honge and splitting will be
double
∆c = 2∆𝑡 (cubic has ML8 and tetrahedral has ML4)

∆𝑂 > ∆𝑐 > ∆𝑡
∆𝑡 → ligand = 4 ; ∆𝑂 → ligand = 6
Ligand = 2/3 of ∆𝑂
Orbital → 2 neeche ; Orbital → 3 neeche
2 2
Overall ∆𝑡 = × ∆𝑂
3 3
4
∆𝑡 = ∆𝑜 = ∆𝑐
9
4
∆𝑐 = 2∆𝑡 = ∆𝑜
9

FACTORS AFFECTING CRYSTAL FIELD SPLITTING

1. Oxidation state of central metal atom
2. Principal quantum number
3. Ligand strength
4. Number of d electrons
5. Number of ligand
6. When direction is same
Jitna jyada d- orbital mei repulsion lagega , utni jyada splitting

More attraction; more repulsion; more splitting
Attraction ∝ splitting
1. Oxidation state of central metal atom
M+ , M2+ , M3+ , M4+ - L- kispe sabse jyada attraction lagayega ?
Answer - M4+
OXIDATION STATE increases ; splitting increases

+4 oxidation state pr sab metal pairing kr rha hai ; not explained by VBT; but CFT
explains, energy difference is very large than electron cannot jump but also the
pairing energy is very high that we can pair electrons
2. PRINCIPLE QUANTUM NUMBER
Chori karna kaha se easy hai ?

Size increases ; electron is more diffused ; sheilding effect decreases ; therefore
more attraction is in 5d . More attraction ; more splitting
3d se 4d mei jaane mei 20 – 30 % increase ho jaata hai ; 4d se 5d mei jaane mei 30

– 40 % increase milta hai
• Therefore, 4d and 5d, always pairing; splitting is more
n increase ; splitting increase

3. LIGAND STRENGTH
C > N > O > Halogens (order of ligand strength)
Strength of ligand increase ; splitting increase
Ques. Splitting kis ki jyada hogi ?
[Fe(NH3)6]2+ ; [Co(NH3)6]3+
Oxidation state increase ; splitting increase ; Fe2+ and Co3+
Answer - [Co(NH3)6]3+
Ques. Splitting kis ki jyada hogi ?

[Fe(NH3)6]2+ ; [Ru(NH3)6]2+
n increase ; splitting increase ; Fe2+ (3d) and Ru2+ (4d)
Answer - [Ru(NH3)6]2+
Question. Compare 3d ka +3 and 4d ka +2 ?
Answer – no comparison
Question. 3d with CN (strong) and 4d with Cl (weak)

Answer. No comparison
4. NUMBER OF d- electrons
When O.S. ; principle quantum number ; ligand – all are same
Then only check number of d-electrons

Ligand will approach 1 easily
Number of d electrons decrease; splitting increase (the difference is about 3-4 % )
O.S. badhne pr pairing ho gyi
4d/5d mei size increase hone pr pairing ho gyi
Strong ligand aane se pairing ho gyi
But number of d electrons is not responsible for pairing
5. NUMBER OF LIGAND (when direction is same)

Consider tetrahedral and cubic – direction is same
As number of ligand increase ; splitting increase

CFSE (CRYSTAL FIELD STABLISATION ENERGY)
Also known as
1. Splitting energy
2. d-d transition
3. Maximum absorption
a. 𝜆 max (wavelength in nm)
b. Energy (wavenumber in cm-1)
Conversion of wavelength to wavenumber
𝟏
Wave number = E = ; 𝝀 = 𝒘𝒂𝒗𝒆𝒍𝒆𝒏𝒈𝒕𝒉
𝝀
Energy in terms of wavenumber to energy in terms of KJ/ mol

1 kJ/mol = 83.7 cm-1
• Octahedral mei d-orbitals T2g and Eg mei split honge ; yaha high spin and low
spin complexes milenge
• Tetrahedral mei d-orbitals E and T2 mei split honge ; yaha sirf high spin
complexes milenge
• High spin – Hund’s ne kaha electron ko high spin mei pehle rakho ; (2s+1) ki
value jyada ho; means ‘s’ ki value jyada ho
• s will be more when more number of electrons are unpaired
• Low spin – that does not follow Hund’s rule

4,5,6,7,8 mei high spin ; low spin dekhna hai
d8 mei dikhta nhi hai pr hota hai
High spin Low spin
d4 T2g3 Eg1 T2g4 Eg0
d8 mei number of unpaired electron is same

Tetrahedral- always high spin e1 2 6 7 T2 3 4 5 8 9 10

CFSE in octahedral complexes
In high spin complexes, mean pairing energy is always zero
CFSE = −𝟎. 𝟒 × 𝑻𝟐𝒈 𝒆 + 𝟎. 𝟔 𝑬𝒈(𝒆) ∆𝒐 + 𝑴𝑷𝑬
CFSE = experimental energy – theoretical energy (or calculated energy)
CFSE is released energy ; always negative
theoretical mei 1 pair hai

experiment mei 3 pair mile
3 – 1 = 2 MPE (Mean pairing energy)

theoretical mei 1 pair
experimental mei 1 pair
mean pairing energy = 1 – 1 = 0
that’s why MPE = 0 in high spin
Note – pairing energy zero nhi hai ; mean pairing energy zero hai

d1 T2g1 Eg0 −0.4 × 1 + 0.6 × 0 ∆𝑜 = −0.4∆𝑜
d2 T2g2 Eg0 −0.4 × 2 + 0.6 × 0 ∆𝑜 = −0.8∆𝑜
d3 T2g3 Eg0 −0.4 × 3 + 0.6 × 0 ∆𝑜 = −1.2∆𝑜
d4(H.S) T2g3 Eg1 −0.4 × 3 + 0.6 × 1 ∆𝑜 = −0.6∆𝑜
d4(L.S) T2g4 Eg0 −0.4 × 4 + 0.6 × 0 ∆𝑜 = −1.6∆𝑜 + 1𝑃. 𝐸.
d5(H.S) T2g3 Eg2 −0.4 × 3 + 0.6 × 2 ∆𝑜 = 0
d5(L.S) T2g5 Eg0 −0.4 × 5 + 0.6 × 0 ∆𝑜 = −2.0∆𝑜 + 2 𝑃. 𝐸.
d6(H.S) T2g4 Eg2 −0.4 × 4 + 0.6 × 2 ∆𝑜 = −0.4∆𝑜
d6(L.S) T2g6 Eg0 −0.4 × 6 + 0.6 × 0 ∆𝑜 = −2.4∆𝑜 + 2𝑃. 𝐸.
d7(H.S) T2g5 Eg2 −0.4 × 5 + 0.6 × 2 ∆𝑜 = −0.8∆𝑜
d7(L.S) T2g6 Eg1 −0.4 × 6 + 0.6 × 1 ∆𝑜 = −1.8∆𝑜 + 1𝑃. 𝐸.
d8 T2g6 Eg2 −0.4 × 6 + 0.6 × 2 ∆𝑜 = −1.2∆𝑜
d9 T2g6 Eg3 Dr. Kuldeep−0.4 × 6CLASS
Garg (KDSIR + 0.6 ×3
NOTES) ∆𝑜 = −0.6∆𝑜 112
HIGH SPIN LOW SPIN
d1 −0.4∆𝑜 −0.4∆𝑜
d2 −0.8∆𝑜 −0.8∆𝑜
d3 −1.2∆𝑜 −1.2∆𝑜
d4 −0.6∆𝑜 −1.6∆𝑜 + 1 𝑃. 𝐸.
d5 0 −2.0∆𝑜 + 2 𝑃. 𝐸.
d6 −0.4∆𝑜 −2.4∆𝑜 + 2 𝑃. 𝐸.
d7 −0.8∆𝑜 −1.8∆𝑜 + 1 𝑃. 𝐸.
d8 −1.2∆𝑜 −1.2∆𝑜
d9 −0.6∆𝑜 −0.6∆𝑜

If experimental pairing energy is given and experimental splitting energy. We can
tell high spin and low spin
• If Pairing energy < splitting
Pairing occurs – low spin
• If Pairing energy > splitting
Pairing occurs – high spin
• If Pairing energy = splitting
Temperature dependent molecules ; HIGH-SPIN LOW-SPIN EQUILIBRIA
If Pairing energy > splitting (paas paas hai ; kum hai distance pair krne ki need nhi
; upar chala jayega
If Pairing energy < splitting (pair karne mei kum energy lg rhi hai ; pair kara do
NOTE – CFS is a number ; can never be negative (distance cannot be negative)
• CFSE is releasing energy (always negative)

• Splitting is never negative
• CFSE in Tetrahedral complexes

CFSE = −𝟎. 𝟔 × 𝑬𝒈 𝒆 + 𝟎. 𝟒 × 𝑻𝟐𝒈(𝒆) × ∆𝒕
𝟒
CFSE = −𝟎. 𝟔 × 𝑬𝒈 𝒆 + 𝟎. 𝟒 × 𝑻𝟐𝒈(𝒆) × ∆𝒐
𝟗
d1 E1 T20 −0.6 × 1 + 0.4 × 0 ∆𝑡 = −0.6∆t

d2 E2 T20 −0.6 × 2 + 0.4 × 0 ∆𝑡 = −1.2∆t
d3 E2 T21 −0.6 × 2 + 0.4 × 1 ∆𝑡 = −0.8∆t
d4 E2 T22 −0.6 × 2 + 0.4 × 2 ∆𝑡 = −0.4∆t
d5 E2 T23 −0.6 × 2 + 0.4 × 3 ∆𝑡 = 0
d6 E3 T23 −0.6 × 3 + 0.4 × 3 ∆𝑡 = −0.6∆t
d7 E4 T23 −0.6 × 4 + 0.4 × 3 ∆𝑡 = −1.2∆t
d8 E4 T24 −0.6 × 4 + 0.4 × 4 ∆𝑡 = −0.8∆t
d9 E4 T25 −0.6 × 4 + 0.4 × 5 ∆𝑡 = −0.4∆t
Ques. Calculate CFSE for [Ti(H2O)6]3+ if maximum absorption is 492 nm

Answer- maximum absorption = 429 nm – wavelength
Ti3+→ d2s2 → d1 → CFSE = 0.4 ∆𝑜
𝜆 max = 492 nm
−
1 1 1 107𝑐𝑚 1
Wavenumber = = = _ = = 20300 cm-1
𝜆 max 492 𝑛𝑚 492 ×10 7𝑐𝑚 492
Splitting = 20300 cm-1
−1 −8120 𝐾𝐽
CFSE = −0.4 × 20300 = 8120 𝑐𝑚 = = − 93 𝑘𝐽/𝑚𝑜𝑙
83.7 𝑚𝑜𝑙
{1kJ = 83.7 cm-1)
Dr. KULDEEP GARG
Ques. Calculate CFSE for [NiCl4]2-. if CFSE for [CoCl6]4-is 10000 cm-1
Answer- Octahedral CFSE se octahedral splitting nikalo fir tetrahedral ki splitting
calculate kro fir tetrahedral ki CFSE calculate kro
This is applied when ligand is same
Metal is in same oxidation state
NOTE – splitting is independent of number of electrons but CFSE is dependent on
number of electrons
Question – Calculate CFSE of [CoCl4]2-. if CFSE for [CoCl6]4-is 10000 cm-1

CFSE = 10000 cm-1
[CoCl6]4-
x – 6 = - 4 ; x = +2
Co2+ → d7 → T2g5 Eg2
−
CFSE = −0.4 × 5 + 0.6 × 2 ∆𝑜 = −0.8∆𝑜 = −10000 𝑐𝑚 1
10000
∆𝑜 = = 12500
0.8
4 4
∆𝑡 = ∆𝑜 = ×12500
9 9
4
CFSE = −0.6 × 4 + 0.4 × 3 ∆𝑡 = −1.2∆𝑡 = −1.2 × × 12500
9
CFSE = - 6666.6 cm-1
Note – maximum absorption means ∆𝑜
Ques. Calculate CFSE for [Cr(H2O)4F2]; if maximum absorption of [Cr(H2O)6]2+ is

10000 cm-1 and [CrF6]4- is 8000 cm-1
[Cr(H2O)6]2+ → Cr2+ → d4 → T2g3 Eg1
CFSE = −0.4 × 3 + 0.6 × 1 ∆𝑜 = −0.6∆𝑜
−
For 6 ligands (H2O) CFSE = −0.6 × 10000 = −6000 𝑐𝑚 1
[CrF6]4- → Cr2+ → d4 → T2g3 Eg1

CFSE = −0.4 × 3 + 0.6 × 1 ∆𝑜 = −0.6∆𝑜
−
For 6 ligands (F) CFSE = −0.6 × 8000 = −4800 𝑐𝑚 1
−6000 −4800
CFSE of [Cr(H2O)4F2] = ×4 + × 2 = −4000 + −1600
6 6
CFSE of [Cr(H2O)4F2] = - 5600 cm-1

Ques. Calculate CFSE for [Cr(CN)4(H2O)2]2-; if crystal field splitting of [Cr(CN)6]4-
is 10000 cm-1 . Pairing energy is 5000 cm-1 and [Cr(H2O)6]2+ is
is 6000 cm-1
• [Cr(CN)6]4-→ Cr2+ → d4 → T2g4 Eg0
CFSE = −0.4 × 4 + 0.6 × 0 ∆𝑜 + 𝑃. 𝐸. = −1.6∆𝑜 + 𝑃. 𝐸.
−
For 6 ligands (CN-) CFSE = −1.6 × 10000 + 5000 = −11000 𝑐𝑚 1
• [Cr(H2O)6]2+ → Cr2+ → d4 → T2g3 Eg1
CFSE = −0.4 × 3 + 0.6 × 1 ∆𝑜 = −0.6∆𝑜
−
For 6 ligands (H2O) CFSE = −0.6 × 6000 = −36000 𝑐𝑚 1
−11000 −3600
• CFSE of [Cr(CN)4(H2O)2]2- = ×4 + ×2
6 6
= −7333.3 + −1200
• CFSE of [Cr(CN)4(H2O)2]2- = - 8533.3cm-1
Ques. Calculate CFSE for [CoL6]2+; where L is neutral monodentate ligand ,
maximum absorption is 18000 cm-1
1. If Pairing energy is 15000cm-1
2. If Pairing energy is 20000cm-1
Calculate CFSE in both cases.
[CoL6]2+→ Co2+ → d7 → T2g6 Eg1
1. CFSE = −0.4 × 6 + 0.6 × 1 ∆𝑜 = −1.8∆𝑜 + 1 P.E.
−
CFSE = −1.8 × 18000 + 15000 = −17400 𝑐𝑚 1
2. Pairing energy > splitting – high spin → T2g5 Eg2

CFSE = −0.4 × 5 + 0.6 × 2 ∆𝑜 = −0.8∆𝑜
−
CFSE = −1.8 × 18000 = −14400 𝑐𝑚 1

OSSE / OSPE
Octahedral site stabilization energy / Octahedral site preference energy
Both the terms are same
Ques. Calculate OSSE for [CoCl6]4- if maximum absorption is 10000 cm-1
OSSE is the difference between octahedral and ttrahedral of same complex
For octahedral, [CoCl6]4-
−
∆𝑜 = 10000 𝑐𝑚 1
CFSE = −0.8 ∆𝑜 = −0.8 × 10000 = −8000
For Tetrahedral, [CoCl4]2-
4 −1
∆𝑡 = × 10000 𝑐𝑚
9
4
CFSE = −1.2 ∆𝑡 = −1.2 × × 10000 = −5333.3
9
OSSE / OSPE = - 8000 + 5333.3 = - 2666.7 cm-1
Hypothetical splitting order of

1. TBP
2. SP
3. PBP
Transition states are hypothetical; that’s why hypothetical splitting order

1. Jaha se direct approach hogi ; uski energy high hogi
2. If attack is not on 900 in the plane that consist two obitals not at 900 say dx2-y2
and dxy ; the attack is from more or less angle and dx2-y2 and dxy ko same
weightage di jayegi
3. If there is not any ligand – energy is lowest
OCTAHEDRAL –
dx2-y2 = dz2 > dxy = dyz = dzx
SQUARE PYRAMIDAL
dx2-y2 > dz2 > dxy > dyz = dzx
Number of attack is less on z axis

TRIGONAL BIPYRAMIDAL
dz2 >dx2-y2 = dxy > dyz = dzx
XY plane mei 1200 ka angle (not 900)
Therefore, dx2-y2 = dxy
PENTAGONAL BIPYRAMIDAL
dz2 >dx2-y2 = dxy > dyz = dzx
Z pr direct attack hai
XY plane mei 720 ka angle (not 900)
Therefore, dx2-y2 = dxy

JAHN TELLER DISTORTION

We will discuss following things
1. Why JTD ?
2. Where JTD ?
3. Types of JTD ?
a. Slight or strong
b. Zin or Zout
c. Dyanamic or static
• Slight – strong ka kya reason hai
• Zin – Zout mei splitting kaisi hogi – JTSE
• Dynamic and static – BSR (berry pseudo rotation)
• Dynamic and static mei transition – spectroscopy based – experimental data
• Temperature dependance – FOT (frozen out and fluxonial out temperature )
• Factors affecting JTD
• Extent of JTD in tetrahedral , TBP , square planar
• Existence – example – [Co(CN)6]4- does not exist ; [Co(CN)5(H2O)]3- exist
• [Cu(en)3]2+ does not exist ; [Cu(en)2(H2O)2]2+ exist
• Disproprtionation reaction of Au2+
❑ What is Distortion?
➢ Change in bond distance
➢ Change in bond angle

STABILITY – THERMODYNAMIC V/S KINETIC
Medicine mangvayi – khaasi hui hai
A ne kaha 100 rupees lagenge ; 3 years ka time do
B ne kaha 10000 rupees lagenge ; 2 days ka time do
We will prefer B
C ne kaha 1000 rupees mei milegi ; 3 days lagenge; we will prefer C
There is no relationship between thermodynamic and kinetic stability
• JTD gives thermodynamic stability and kinetic lability
thodi si energy dete hi upar neeche ka bond toot
k reaction karenge ; fastly
higher JTD ∝ thermal stability
higher JTD ∝ kinetic lability
Experimental = theoretical + CFSE + JTSE

1500 = 1000 (mrp) + 490 (GST + transport) + 10
JTSE is microscopic
WHY JTD ?
M-L inhe geometry se koi lena dena nhi hai ; maximum ligand chahiye metal ko
Metal – ghr mei 2 bache h ; dance kr rhe hai ; masti kr rhe hai … mamma ko gussa
aaya ; ek teacher ko bulaya ; dono bache aaram se beth gye
Bache = electrons of metal ; Dance = electronic degeneracy ; Ligand = teacher

Metal ligand se jud k apni degeneracy khatam krna chahta hai
• Half filled – no degeneracy
• Fully filled – no degeneracy
• Non filled – no degeneracy
• Jitni jyada splitting ; utna jyada destablise

L+S ki value jyada ; coupling jyada ; jyada destablise
• JTD – to remove electronic degeneracy
• WHERE JTD ?
• Jaha degeneracy wala JTD
HIGH SPIN LOW SPIN
d2 T2g2 Eg0 T2g2 Eg0 BLUE COLOUR WALO
MEI DEGENERACY
ABSENT HAI
d5 T2g3 Eg2 T2g5 Eg0 YELLOW COLOUR
WALO MEI
DEGENERACY PRESENT
d7 T2g5 Eg2 T2g6 Eg1 HAI

Eg or T2g mei se koi ek bhi unsymmetrical ho toh JTD present hogi
Eg or t2g dono symmetrical ho toh no JTD
Aisa B.Sc. Mei padhte hai
If CFSE = 0 ; JTSE = 0
If CFSE = maximum ; JTSE = 0
If CFSE = maximum/2 ; JTSE = 0
• If degeneracy is present at that position, where ligand do direct attack; distortion
is high
• Thoda bohat farak padta hai … agar pados mei shaadi ho toh thoda bohat
excited hum bhi honge ; dx2-y2 ki energy jyada hui ; dxy ki energy bhi thodi
increase ho jayegi

• If T2g has electronic degeneracy – slight distortion
• If Eg has electronic degeneracy – strong distortion
HIGH SPIN LOW SPIN
d1 SLIGHT SLIGHT
d2 SLIGHT SLIGHT
d3 NO NO
d4 STRONG SLIGHT
d5 NO SLIGHT
d6 SLIGHT NO
d7 SLIGHT STRONG
d8 NO NO
d9 STRONG STRONG
Zin and Zout

Zout – ligand dx2-y2 se aana chahte hai
More attraction of ligands with metal
More attraction ; more repulsion
dz2 door ho gya
And z ki energy kum ho gyi ; z ka bond door
Zin – ligand dz2 se aana chahte hai

More attraction of ligands with metal
More attraction ; more repulsion
And z ki energy jyada ho gyi ; xy ka bond door
NOTE- number of unpaired electrons remains same
Before and after distortion

❑ d1 – T2g1 Eg0
Exp. energy = theoretical + CFSE + JTSE
1
Exp. energy = (-x) + (-0.4 ∆𝑜) + − 𝛿2 → Zout
3
2
Exp. energy = (-x) + (-0.4 ∆𝑜) + − 𝛿2 → Zin (more)
3
JTSE ∝ STABILITY
❑ d2 – T2g2 Eg0
2
Exp. energy = (-x) + (-0.8 ∆𝑜) + − 𝛿2 → Zout (more)
3
1
Exp. energy = (-x) + (-0.8 ∆𝑜) + − 𝛿2 → Zin
3
❑ d3 – T2g3 Eg0
Exp. energy = (-x) + (-1.2 ∆𝑜) + 0𝛿2 → 0
Pehle hi degenracy nahi hai ; therefore distortion nhi hai
❑ d4 – T2g3 Eg1
1
3
1
3
Same in both Zin and Zout

DRAWBACK OF JTD
JTD ne sirf itna bta diya ki distortion hai … but konsa hai … nahi bataya
NO QUALITATIVE DATA
Aur agar dono mile toh konsa kitna hoga ye bhi nhi bataya
NO QUANTITATIVE DATA
• If Zout/Zin both are coming ; give preference to Zout > Zin
❑ d4 (low spin)– T2g4 Eg0

1
3
2
Exp. energy = (-x) + (-1.6 ∆𝑜) + − 𝛿2 → Zin (more)
3
Theoretically, we can determine Zin or Zout in complexes with slight distortion
Agar strong distortion hai toh Zin/Zout nhi bta skte ; mostly Zout is preffered
❑ d5 (high spin) – T2g3 Eg2 →no degeneracy

❑ d5 (low spin) – T2g5 Eg0
2
Exp. energy = (-x) + (-2 ∆𝑜) + − 𝛿2 → Zout(more)
3
1
Exp. energy = (-x) + (-2 ∆𝑜) + − 𝛿2 → Zin
3
❑ d6 (high spin) – T2g4 Eg2

1
3
2
Exp. energy = (-x) + (-0.4 ∆𝑜) + − 𝛿2 → Zin(more)
3
❑ d6 (low spin) – T2g6 Eg0 →no degeneracy
❑ d7 (high spin) – T2g5 Eg2

2
Exp. energy = (-x) + (-0.8 ∆𝑜) + − 𝛿2 → Zout(more)
3
1
3

❑ d7 (low spin) – T2g6 Eg1
1
3
1
3
Same in both Zin and Zout ; cannot explain
❑ d8 – T2g6 Eg2 →no degeneracy

❑ d9 – T2g6 Eg3 →no degeneracy
1
3

1
3
Same in both Zin and Zout ; cannot explain
DYNAMIC AND STATIC DISTORTION

Dynamic and static are experimental
Dynamic – kabhi Zin kabhi Zout
Static – if Zout remain Zout ; if Zin remain Zin
• Slight distortions are dynamic ;
• Strong distortions are static (but if ligands are NO2 , NO3 , NO+ with strong
distortion behave as dynamic)
• Static is found only in those compounds found in lattice

➢ [Cr(H2O)6]2+ and [Cr F6]4- Which one will show dynamic JTD?
➢ [Cr(H2O)6]2+→ Cr2+ → d4 → strong JTD
➢ But not in lattice ; therefore show dynamic
➢ [Cr F6]4-→ Cr2+ → d4 → strong JTD ; lattice mei hai – show static
➢ NOTE – strong distortions mei agar lattice energy wala hai toh voh static hi
dikhayega … but agar lattice energy wala nhi hai ; hydration energy wala hai
toh strong distortion hone pr bhi dynamic dikhane ki tendency rakhta hai
➢ Ques. Which of the following does not show dynamic JTD

a) [Cu(H2O)6]2+
b) [Ti(H2O)6]3+
c) [Fe(H2O)6]2+
d) [Cr F6]4-
Answer – (d) [Cr F6]4-
➢ Ques. Which of the following can show static JTD

a) [Cr(H2O)6]2+
b) [Ni(H2O)6]2+
c) [FeF6]3-
d) [Mn(H2O)6]2+
Answer – (a) [Cr(H2O)6]2+→ Cr2+ → d4 → strong JTD
(b) d8 (c) d5 (d) d5 no JTD

❑ [Ti Cl6]3- and [Ti(H2O)6]3+
➢ [Ti Cl6]3- → Ti3+ → d1 → static
➢ [Ti(H2O)6]3+→ dynamic
EXCEPTIONS (LEARN)
➢ [Cu(H2O)6]2+→ Zout
➢ [Cu(NO2)6]4-→ all bond length equal
➢ [Ti Cl6]3- → Zin
➢ [Ti(H2O)6]3+→all bond length equal
➢ [Cr F6]4- → Zout
➢ [Mn F6]3- → 2,2,2 distortion

[Cu(NO2)6]4-→ all bond length equal at room temperature
Berry pseudo rotation at room temperature
[Cu(NO2)6]4-→ at 298 K → all bond length equal → dynamic

[Cu(NO2)6]4-→ freeze kr diya ;we get static distortion
The temperature at which we get static distortion is known as FROZEN OUT
TEMPERATURE (FOT)
• FOT is changing because of change in counter metal with (NO2)
FOT
1. Tl2Pb[Cu(NO2)6] 245
2. K2Pb[Cu(NO2)6] 273
3. Rb2Pb[Cu(NO2)6] 276
4. Cs2Pb[Cu(NO2)6] 285
All are dynamic at room temperature ;
1. Tl2Pb[Cu(NO2)6]
2. K2Pb[Cu(NO2)6]
3. Rb2Pb[Cu(NO2)6] berry pseudo rotation increases
4. Cs2Pb[Cu(NO2)6]

Tl (p-block ; ionic) K; Rb ; Cs (s-block ; ionic)
Order of ionic character – K < Rb < Cs
Therefore, Tl < K < Rb < Cs (IONIC CHARACTER)
Covalent character ka order exactly opposite hoga ionic character k order se
• Tl2Pb[Cu(NO2)6]
• M’ [M-L] – M’ has covalent character more ; [M-L] has covalent character
• If covalent character is more; BSR (berry pseudo rotation) is more; Temperature
is very far from room temperature ;
• Jitna jyada covalent character utna jyada berry pseudo rotation; utna jyada
temperature dena pdega rotation rokne k liye ; FOT decreases
• More ionic character ; more frozen out temperature
➢ d9 → Zin / Zout ye kaise btayenge; on the basis of hints in question
• HINT – if higher energy orbital = dx2-y2 ; if unpaired electron is in dx2-y2
• Other names – Zin = tetragonally compressed
• Zout = tetragonally elongated
JAHN TELLER DISTORTION in Tetrahedral and TBP
GATE – [CuCl5]3- TBP geometry mei exist krta h ; JTD k baad kya hoga ?
a) 3 long ; 2 short
b) 2 long; 3 short
c) All equal
d) None of these
TBP = dz2 > dx2-y2 = dxy > dyz = dzx

Answer – (a) 3 long ; 2 short
Ligand will come from dz2 – more attraction

[Fe O4]2- → Fe6+ → d2

[Fe O4]4- → Fe4+ → d4
POINT GROUP
JTD NO JTD
Oh D4h Oh
Td D2d Td
TBP D3h D3h

DISPROPORTION of Au+2

Some special cases
• NO2 / NO3 / NO+ → dynamic
• [Co(CN)6]4- → not exist but [Co (H2O)(CN)5]3- → exist ; WHY ?
a) Due to weak ligand H2O
b) Due to JTD
c) Due to mixed weak and strong ligand
d) None of these
Answer – (b) due to JTD
[Co(CN)6]4- →Co2+ → d7
[Co (H2O)(CN)5]3-
CFS ∝ JTS ∝ JTD ∝ Thermodynamic stability
Factors affecting CFS will affect JTD
• Higher Oxidation state → higher thermal stability
• Higher principal quantim number – thermal stability
• Higher strength of ligand – thermal stability
• [Co(CN)6]4- and [Co (H2O)(CN)5]3- - higher JTD ?

Answer - [Co(CN)6]4-
CN is a good pi – acceptor , pi – bonding character ;
tension is created ; Therefore, change one ligand by H2O
• [Co (H2O)(CN)5]3- - distortion pehle se kamm ho gya
• [Co (H2O)(CN)5]3- is stable

CRYSTAL FIELDSPLITTING OF SQUARE PLANAR COMPLEX
By the help of JTD also known as potential JTD or pseudo JTD

Splitting of square planar in 4d and 5d
Eg ki splitting bohat jyada badh jaati hai

Strong distortion walo mei nhi bta paaye Zin/Zout konsa hoga
If no hint is given – mark Zout
If hint is given – 1. spliting based ; 2. reactivity based
d4 High spin – unpaired electron in
1. dx2-y2 = Zin
2. dz2 = Zout
❑ APPLICATIONS OF CFSE
1. Spinal
2. Ionic radius
3. Lattice energy
4. Hydration energy
[Co Cl6]4- Experimental = theoretical + CFSE
- 1500 = - 1000 + 500
Co-Cl → -1000 theoretically release kr rha hai pr experimental energy thodi jyada
hai ; toh shayad humne radius maan li hogi aur real mei choti hogi ; lattice energy
is inversely proportional to r ; hydration is inversely proportional to r
The experimental , theoretical and CFSE all are a kind of lattice energy
❑ SPINALS
We have to study spinals of d-block element – d0 to d10
Spinals are mixed oxides of metal
Example – FeO. Fe2O3 = Fe3O4; NiO.Cr2O3 = Fe3O4;
(Fe2+) (Fe3+)
General formula of spinal – AB2O4 and A3O4 (AA2O4)
ABCO4 is also found now ; books mei nhi aaya abhi
• A can be s-block , d-block, f-block, rarely p-block → +2 wale
• B can be d-block, p-block, f-block → +3 wale
➢ s-d block spinal → MgFe2O4
➢ d-d block spinal → Fe3O4 ; NiCr2O4
➢ f-d block spinal → YbFe2O4
➢ p-d block spinal → XeFe2O4
➢ d-p block spinal → FeAl2O4
➢ d-f block spinal → FeGd2O4
➢ All spinals here are containing d-block – abhi itna hi padhna hai

• AB2O4
Charge : x + 2y – 8 = 0
x + 2y = 8
+2 +2(+3) = 8 ; A2+ and 2 B3+ (in voids 0
T O L
• FCC has 2 types of voids
2 1 1
1. Octahedral voids
2. Tetrahedral voids
L = 4 for FCC – lattice point contain = 4 oxygen
Tetrahedral voids = 8
Octahedral voids = 4
12 voids contain A2+ and 2 B3+

Spinals are of two types

1. Normal spinals
2. Inverse spinals
NORMAL SPINALS – based on electroneutrality principle

A2+ - in tetrahedral voids
B3+ - in octahedral voids
Definition – if A2+ are present in tetrahedral voids; all B3+ are present in octahedral
voids
BOAT – normal ; B3+ - in octahedral voids ; A2+ - in tetrahedral voids

If A2+ ion occupy 1/8 th of the tetrahedral voids and if two B3+ ions occupy ½ of
the octahedral voids – NORMAL
Size of octahedral void is larger than that of tetrahedral void
Size of A2+ is more than that of B3+
❑ INVERSE SPINALS
Based on CFSE –
A2+- in octahedral voids ; B3+ - in octahedral void; B3+- in tetrahedral void
If A2+ and B3+ ion occupy 1/2 of the octahedral voids and one B3+ ion occupy 1/8th
of the tetrahedral voids – INVERSE
• A2+ ko octahedral void mei rakhne se jyada CFSE mil rhi thi

KEY POINTS
➢ All Zn2+ spinals are always NORMAL
➢ All Cr3+ spinals are always NORMAL
➢ Fe3+ spinals are inverse spinals except ZnFe2O4
➢ Al3+ spinals are normal spinals except Al Ni {NiAl2O4 is inverse}
➢ Co3+ with O are normal spinals
➢ Rest all are normal spinals
➢ Key points se pehle CFSE check kr lo

➢ A2+ ki CFSE octahedral mei agar B3+ ki CFSE (octahedral mei ) se jyada hui toh
INVERSE
➢ Example – Mn3O4 ; CoFe2O4
❑ Mn3O4
Mn2+ (High spin) – d5 CFSE = 0
Mn3+ (High spin) – d4 CFSE = - 0.6
CFSE is more of Mn3+ in octahedral ; NORMAL SPINAL
❑ CoFe2O4
Co2+ (High spin) – d7 CFSE = - 0.8
Fe3+ (High spin) – d5 CFSE = 0
CFSE is more of Co2+ in octahedral ; INVERSE SPINAL

Type of Spinal Type of Spinal
MgAl2O4 Normal ZnCo2O4 Normal
MnAl2O4 Normal FeAl2O4 Normal
NiAl2O4 Inverse ZnAl2O4 Normal
MgCr2O4 Normal MnCr2O4 Normal
FeCr2O4 Normal CoCr2O4 Normal
NiCr2O4 Normal CuCr2O4 Normal
ZnCr2O4 Normal MgFe2O4 Inverse
MnFe2O4 Inverse Fe3O4 Inverse
CoFe2O4 Inverse CuFe2O4 Inverse
ZnFe2O4 Normal Mn3O4 Normal
ZnMn2O4 Normal Co3O4 Normal
❑ SPINAL PARAMETER (𝜆)
+
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐵3 𝑖𝑜𝑛 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑖𝑛 𝑡𝑒𝑡𝑟𝑎ℎ𝑒𝑑𝑟𝑎𝑙 𝑣𝑜𝑖𝑑𝑠
• 𝜆= +
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐵3 𝑖𝑜𝑛 𝑖𝑛 𝑙𝑎𝑡𝑡𝑖𝑐𝑒
1
• 𝜆𝑚𝑎𝑥 = = 0.5 (complete inverse)
2
• 𝜆𝑚𝑖𝑛 = 0 (normal spinal)
𝜆
• Inverse character = × 100
0.5
0.5
• If 𝜆 = 0.5 ; inverse character = × 100= 100 %
0.5
• Agar 𝜆 ki value 0 to 0.5 k beech mei lie krti hai toh spinal ko inverse spinal
kahenge but with mixed character
• Spinals with mixed character are – FeMg ; FeMn; AlNi
• MgFe2O4 - 𝜆 = 0.45
• MnFe2O4 - 𝜆 = 0.15
• NiAl2O4 - 𝜆 = 0.4
• Thoda sa inverse character aaya toh inverse hi hoga
❑ TABLE OF VALUES OF 𝜆
+3/+2 Mg Mn Fe Co Ni Cu Zn
Al 0 0 0 0 0.38 - 0
Cr 0 0 0 0 0 0 0
Fe 0.45 0.15 0.5 0.5 0.5 0.5 0
Mn - - - - - - 0
Co - - - 0 - - 0

Tetrahedral Octahedral
A2+ 2 B3+ Normal
B3+ 1 B3+ Inverse
1 A2+ 100%
0.5 B3+ 0.5 B3+ + 1 B3+ Inverse
0.5 A2+ 0.5 A2+ 50%
4 types k question pooch sakte hai

1. % occupancy of A2+ in tetrahedral voids
2. % occupancy of A2+ in octahedral voids
3. % occupancy of B3+ in tetrahedral voids
4. % occupancy of B3+ in octahedral voids

Question. Calculate % occupancy of Ni2+ ion in octahedral voids in a spinal
NiAl2O4 if 𝜆 = 0.4 . {GATE}
𝜆 0.4 4
Inverse character = × 100 = × 100 = × 100 = 80%
0.5 0.5 5
Ni2+ 2 Al3+ Normal
0.2 Ni2+ 0.8 Ni2+ Inverse
0.8 Al3+ 0.2 Al3++ 1 Al3+ 80%
fraction of ion in the void

% occupancy of ion in voids = × 100
total number of voids
0 .8
% occupancy of Ni2+ in oh voids = × 100 = 20%
4

0 .2
• % occupancy of Ni2+ in Td voids = × 100 = 2.5%
8
0 .8
• % occupancy of Al3+ in Td voids = × 100 = 10%
8
1 .2
• % occupancy of Al3+ in oh voids = × 100 = 30%
4
• Question. Calculate % occupancy of Fe3+ ion in tetrahedral voids in a spinal
MnFe2O4 if 𝜆 = 0.15 .
(a) 2.75% (b) 3.75% (c) 4.75% (d) 5.75%
𝜆 0.15
Solution - Inverse character = × 100 = × 100 = 30%
0.5 0.5
Mn2+ 2 Fe3+ Normal
0.7 Mn2+ 0.3 Mn2+ Inverse
0.3 Fe3+ 0.7 Fe3++ 1 Fe3+ 30%
0 .3
• % occupancy of Fe3+ in Td voids = × 100 = 3.75%
8
Answer – (b)
HYDRATION AND LATTICE ENERGY
• Experimental Hydration energy = Theoretical H.E. + CFSE

• Experimental Lattice energy = Theoretical L.E. + CFSE
• Here radius is the distance divided by 2

• And distance is the distance between M and L

For d0 ; theoretical = experimental

• For d1
Incoming ligand ka effect padega radius pr
Theoretical mei Effect of electron hai
Experimental mei nhi h electron ka effect
One extra proton increases the attraction
Theoretical radius > experimental radius
• For d2
Electron ka koi effect nhi ;
2 proton se jyada attraction hua ;
Radius kum hogi

• For d3
Electron ka koi effect nhi ; 3 proton se jyada
attraction hua ; Radius kum hogi
• For d4
Electron ka effect padega ; repulsion increases
Radius increases; theoretical mei 2 electron
Interfere kr sakte hai ligand k raaste mei lekin
experimental mei ek electron interfere karega
• For d5
Same effect of electron in theoretical and
Experimental
Theoretical Experimental Theoretical Experimental
d0 100 pm 100 pm d3 97 pm 94 pm
d1 99 pm 98 pm d4 96 pm 95 pm
d2 98 pm 96 pm d5 95.5 pm 95.5 pm

LIGAND FIELD THEORY

(MOLECULAR ORBITAL THEORY)
LFT- quantum mechanics se aayi hai ; yha hum wave functions ki baat krte hai
Hybrid orbital ka wave function pooch lete hai ; ya normalisation constant pooch
lete hai
• NMR/NQR / nephelauxetic effect/ ESR – sabse pta chla ki covalent nature hai
• VBT ne kaha ki bonding ki energy 2 jagah split ho gyi ;
• Question is bonding ki energy increase kaise kr rhe ho

Ligand pooch rhe hai ; jab bonding nhi kr rhe toh splitting pr kaise effect daala
➢ TWO DRAWBACKS OF CFT
1. Bonding orbital hone k baad bhi Eg ki energy kyo badhi
2. Strong ligand se pairing. Why ?
LFT ko 2 tareeke se padh sakte hai – quantum and bonding (MOT)

• All three theories are based on geometry
• Geometry hume pta hai – octahedral fixed hai ; diagram bnao
• Ligands six directions se (+) phase mei aayega
• S- center se sabse saath bonding bna rha hai
• Ab hum wavefunction of s orbital likhenge

Wave function of s – orbital
1
𝜓𝑠 = 𝜎𝑥 + 𝜎 − 𝑥 + 𝜎𝑦 + 𝜎 − 𝑦 + 𝜎𝑧 + 𝜎 − 𝑧
6
1
is the normalisation constant ;
6
• Normalisation constant kaise nikala ?
• sabke saamne k constant ka sqaure kro – 12 + 12 + 12 + 12 + 12 + 12 =6
1 1
• Ab iss value ko mei put kr do = Normalisation constant =
6
1
• 𝜓𝑝𝑥 = 𝜎𝑥 − 𝜎 − 𝑥
2
• Normalisation constant = 12 + (-1)2 =2
• Negative sign kuki antibonding bna h

1
• 𝜓𝑝𝑦 = 𝜎𝑦 − 𝜎 − 𝑦
2
1
• 𝜓𝑝𝑧 = 𝜎𝑧 − 𝜎 − 𝑧
2
1
• 𝜓𝑑𝑥2 − 𝑦2 = 𝜎𝑥 + 𝜎 − 𝑥 − 𝜎𝑦 − 𝜎 − 𝑦
4
• x pr positive ; y pr negative
• 12 + 12 + (-1)2 + (-1)2 =6
• 𝜓𝑑𝑧2 − 𝑥2 = 𝜎𝑧 + 𝜎 − 𝑧 − 𝜎𝑥 − 𝜎 − 𝑥
• 𝜓𝑑𝑧2 − 𝑦2 = 𝜎𝑧 + 𝜎 − 𝑧 − 𝜎𝑦 − 𝜎 − 𝑦
1
• 𝜓𝑑𝑧2 = 2𝜎𝑧 + 2𝜎 − 𝑧 − 𝜎𝑥 − 𝜎 − 𝑥 − 𝜎𝑦 − 𝜎 − 𝑦
2 3
• 22 + 22 + 12 + 12 + 12 + 12 =4 + 4+1+1+1+1=12
1 1
• Normalisation constant = =
12 2 3
Orbital s px py pz 𝑑𝑥2 − 𝑦2 𝑑𝑧2
Normalisation constant 1 1 1 1 1 1
6 2 2 2 2 2 3
LIGAND FIELD THEORY

Ligand make group orbitals called LGOs Ligand Group Orbital
• LGOs bind with metal
• Metal(wife) ko kaha ligand (guests) aa rhe hai ; metal asks kitne aayenge ;
ligands 6 aa rhe hai … bethne k liye 6 stools lga diye … ligand bina nakhre kre
beth jayenge stool pr chota ho ya bada ho … ligands will adjust their symmetry
according to the available symmetry of metal
• Identity of individual ligand is vanished ; all are similar (baarati) sabko ek jaisa
ku banaya … kuki ek ligand pehle chla jaata toh s-ortibal (gol gappe) sab
khatam kr deta
KEY POINTS
• S-orbitals ka bonding sabse neeche hoga
• P-orbital ka anti-bonding sabse upar hoga
• In octahedral
dxy, dyz, dzx t2g

dx2-y2 , dz2 eg
S a1 g
p t1u
• This is from character table of octahedral

• Sigma bond is made by eg orbitals
• t2g is not involved in sigma bond
• Number of bonding M.O. = a1g + t1u + eg = 1 + 3 + 2 = 6
• Number of anti-bonding M.O. = eg* +a1g* + t1u* = 2 + 1 + 3 = 6
• Number of non-bonding M.O. = t2g = 3
• Total number of molecular orbitals = 6+6+3 = 15
• Order of energy = a1g < t1u < eg < t2g < eg* < a1g* < t1u*
• Only sigma bonding mei Δ𝑜 kis kis ka gap hai ?
• Answer – this is a d-d transition
• Δ𝑜 = t2g → eg*
• Δ𝑜 = nb → σ*
• Eg. [Co(NH3)6]2+ and [Co(en)3]2+

Octahedral with sigma and pi bonding
π-donor π-acceptor
• Wants nb empty • Want nb filled
• If ligand is π-donor- splitting kum • If ligand is π-acceptor- splitting

ho jaati hai increase ho jaati hai


• Δ𝑜 = t2g* → eg* • Δ𝑜 = t2g → eg*

• Δ𝑜 = π* → σ* • Δ𝑜 = π → σ*
• Transition is d-d transition • Transition is d-d transition
Only σ donor π-donor π-acceptor

Δ𝑜 t2g → eg* t2g* → eg* t2g → eg*
nb → σ* π* → σ* π → σ*

❑ MOD of Tetrahedral
dxy, dyz, dzx , px, py, pz t2
dx2-y2 , dz2 e
s a1
❑ t2→ bonding same bnega p and d ka

❑ But antibonding alag – alag bnege with characters of p and d
Dr. KULDEEP GARG

MOD OF TETRAHEDRAL

Color of Co-ordination compound

Visible range – 400 to750 approx.
If compound absorb visible range and give complementary color in visible range
and appear colorful
Color mei hum 3 cheeze padhenge
1. Color type
2. Which transition
3. Color intensity
COLOR TYPE – blue, green , yellow , red etc. – depends on konsi wavelength
absorb kri hai
WHICH TRANSITION
• d-d transition
• Charge transfer
➢ LMCT
➢ MLCT
➢ MMCT
➢ LLCT
COLOUR INTENSITY
Always comparative

You have t shirts of sizes L , XL, XXL
Agar hume kuldeep sir ko t shirt deni hai ; hume nhi pta konsa size de
Similarly single compound ka color aise nhi bta payenge ; UV machiene lao
If we have to givethe same 3 T-Shirts to 15 year old kid; kuldeep sir and khali the
great ; ab hume pta h ki L size wale 15 year old boy ko denge ; XL size kuldeep sir
ko de denge ; XXL size khali the great ko de denge

WAVELENGTH COLOUR COMPLEMENTARY
ABSORBED COLOR
< 400 nm UV Colorless
Wavelength increases
400 – 450 nm Violet Yellow
Energy decreases
450 – 490 nm Blue Orange
490 – 550 nm Green Red
550 – 580 nm Yellow Violet
580 – 650 nm Orange Blue
650 – 750 nm Red green

Question- Match the appropriate color of the following compounds
[M(H2O)6]2+ , [M(en)3]2+ , [MBr6]2+
Color is due to d-d transition
HINT- question mei diya hai ki colour d-d transition ki wajah se h
Therefore, answer is based on splitting

Colors are blue, green and red ; M is any metal of 3d series
• Strength of ligand = en > H2O > Br
• Splitting = en > H2O > Br
• Energy absorb = en > H2O > Br
• Order of energy of color absorbed = Green > Orange > Red
• Complementary color Red Blue Green
• Blue → orange ; green → red ; red → green

• [M(en)3]2+ → red
• [M(H2O)6]2+ → Blue
• [MBr6]2+→ green

Question. [CoL6]3+ is red in color whereas [CoL’6]3+ is green in color, then
L and L’ respectively
(a) NH3 and H2O
(b) NH3 and 1,10-Phen
(c) H2O and 1,10-Phen
(d) H2O and NH3
L L’
Red green → complementary
Green red → absorb
Energy – green > red Dr. KULDEEP GARG
Splitting – L > L’ ; L is stronger than L’
Answer (a) NH3 and H2O
Question – match the items in the three columns
I II (VISIBLE) III(ABSORBED)
A – [Ni(H2O)6](NO3)2 I-Blue X- 675 nm
B – [Ni(NH3)6](NO3)2 II-green Y- 565 nm
A – [Ni(en)6](NO3)2 III- violet Z- 615 nm
(a) A – II – X , B – I – Z , C – III – Y
(b) A – III – Y , B – I – Z , C – II – X
(c) A – I – X , B – II – Y , C – III – Z
(d) A – I – X , B – II – Z , C – III – Y
Strength of ligand = en > H2O > Br

Order of energy of color absorbed = Yellow > Orange > Red
Complementary color Violet Blue Green
C-III ; B – I ; A – II
Answer (a) A – II – X , B – I – Z , C – III – Y
TRANSITION RESPONSIBLE FOR COLOUR IN COORDINATION

1. d-d transition
2. Charge transfer
➢ LMCT
➢ MLCT
➢ MMCT
➢ LLCT
• d1 to d9 except d6 , d7 low spin octahedral – d-d transition
• d0 and d10 ; d6 and d7 – low spin – charge transfer
• d0 → LMCT
Eg. KMnO4 ; CrO42- ; VO43- ; TiO44-
• d10 → LMCT or MLCT – differentiate by ligand
If ligand is π-donor → LMCT ; Eg. ZnO, CdS, CdCl2, CdBr2, CdI2
If ligand is π-acceptor → MLCT ; eg. Ni(CO)4 → d10 converted
• d6 and d7→ Low spin → MLCT because ligand is π-acceptor (if only ML type)
Otherwise
Fe4[Fe(CN)6] → MLCT
K Cr [Fe(CN)6] → MMCT
If two metals are present like this that can show variable oxidation state and are
present in different oxidation state → MMCT
Fe4[Fe(CN)6] → color is due to MMCT
LLCT – where π-π* transition is there (mainly studied in bioinorganic eg.
Porphyrin ring)
❖ TcO4- ; x – 8 = - 1 ; x = +7 ; d5s2 → d0 → LMCT

❖ HgO ; Hg2+ → d10 → π-donor → LMCT
❖ CdS ; Cd2+ → d10 → π-donor → LMCT
❖ ScO45- ; x – 8 = - 5 ; x = +3 ; Sc3+ → d0 → LMCT
❖ [Ti(H2O)6]3+ ; Ti3+ → d1 → d-d transition
❖ [Cr(H2O)6]3+ ; Cr3+ → d4s2 → d3 → d-d transition
❖ CdO ; Cd2+ → d10 → π-donor → LMCT
❖ Cr(CO)6 ; Cr0 → d4s2 → d6 Converted → MLCT
❖ Fe(CO)5 ; Fe0 → d6s2 → MLCT (learn TBP)
❖ CdCl2 ; Cd2+ → d10 → π-donor → LMCT
INTENSITY OF COLOUR
Intensity depends upon number of transition (number of electrons transfer) or
population difference in a particular time studied using BORN OPPHENER
APPROXIMATION METHOD
Intensity depends on major factors – laporte allowed ; spin allowed

Laporte (mom) Spin (dad) Intensity
Allowed allowed 100%
Partially allowed Allowed 90%
Forbidden Allowed 70%
Allowed Forbidden 40%
Partially allowed Forbidden 30%
forbidden Forbidden 20%
Kahi jaana ho toh mom ki permission secondary hai ; dad ki jaroori chahiye hi
chahiye

Intensity is asked only when same wavelength is absorbed

Major factors – laporte allowed; spin allowed
Minor factors – p-d mixing ; JTD ; different ligand ; ligand – ligand repulsion
When major factors cannot explain the intensity; then only go to minor factors
LAPORTE ALLOWED :- ∆𝑙 = ±1
SPIN ALLOWED :- ∆𝑠 = 0
In organic chemistry, color is due to g ↔ u

g-g → not possible transition
u-u → not possible transition
g ↔ u possible transition [Laporte allowed]
LAPORTE ALLOWED :- ∆𝒍 = ±𝟏
s ↔p; p ↔d; d ↔f
s p d f
g u g u
s to f is possible but we will not see any color ; visible region se bahar chla jayega
• If electron changes its spin while transition – colour will not be so intense
• If spin of electron does not change while transition – colour is intense

NOTE – all transitions are spin allowed except d5 high spin or tetrahedral
• Spin allowed is given more priority than spin forbidden
• Therefore; d5 wale hamesh less intense hoga
• Jitna jayda laporte ; utna jyada intense
• Laporte allowed – all charge transfers except MMCT

• Laporte forbidden – all d-d transition and MMCT
• Charge transfer > d-d transition (INTENSITY)

• ∆𝑙 = ±1 ∆𝑙 = 0
• ∆𝑠 = 0 ∆𝑠 = 0 and ∆𝑠 ≠ 0 for d5

d-d transitions : octahedral (ignore d5 High spin) ; ∆𝑙 = 0, ∆𝑠 = 0
tetrahedral (ignore d5) ; ∆𝑙 = 0, ∆𝑠 = 0
Ab minor factors dekhenge
MINOR FACTORS ARE
1. Permanent p-d mixing
2. Permanent different ligand
3. JTD (strong + weak)
4. Ligand-ligand repulsion
❑ P-d mixing
∆𝑙 = ±1 laporte allowed ;
pd mixing is found in tetrahedral
Therefore, tetrahedral will give intense colour than octahedral due to pd mixing
∆𝑙 = ±1 partially laporte allowed
Ques. KMnO4 ; [Co Cl4]2-; [Ti (H2O)6]3+ Order of intensity ?

Mn+7 → d0 → charge transfer
Co+2 → d7 (high spin) → d-d transition (tetrahedral)
Ti+3 → d1 → d-d transition (octahedral)
Intensity = KMnO4 > [Co Cl4]2-> [Ti (H2O)6]3+
Ques. If both are tetrahedral [Co Cl4]2-and [Co Cl2 Br2]2-

CONCEPT – jitna jyada disymmetric or center of symmetry distorted ; p-d mixing
jyada hogi
Intensity = [Co Cl4]2- < [Co Cl2 Br2]2- (number of ligands are more)
3. PERMANENT LIGAND-LIGAND REPULSION

A = [Co Cl4]2- , B = [Co Cl2 Br2]2-; C = [Co Br4]2-
Order of intensity = B > C > A
Br-Br repulsion (ligand-ligand repulsion ) is more ; more dissymetric ; more p-d
mixing ; more laporte allowed ; more intensity
Tetrahedral mei JTD nhi padhte
OCTAHEDRAL – no permanent p-d mixing

ques. Why square plannar are very less intense ?
Because mixing is s-d mixing – g-g mixing
Transition is from d tp sd ; g to gg (very less intense)
1. PERMANENT DISSYMETRIC MOLECULE (different ligand hoga toh jyada

intense color hoga
2. JTD – strong/weak – strong li intensity > weak ki intensity
3. L-L repulsion – jitna jyada bulky utna jyada intense
Ques. A = K2CrO4 ; B = MnCl42- ; C = [Mn(H2O)6]2+ ; D = [Co Cl4]2- , E = [Cr

(H2O)6]2+ ; F = [Cu (H2O)6]2+ ; G = [Cu (en)2 (H2O)2]2+ ; H = [Co Cl3Br]2-
A = K2CrO4 ; CrO42- → Cr+6 → d0 → charge transfer LMCT

B = MnCl42-; Mn+2 → d5 (high spin) → d-d transition ; laporte forbidden ; spin
forbidden
C = [Mn(H2O)6]2+ ; Mn+2 → d5 (high spin) → d-d transition ; laporte forbidden ;
spin forbidden
D = [Co Cl4]2- ; Co+2 → d7 (high spin) → d-d transition
E = [Cr (H2O)6]2+ ; Cr+3 → d3 → d-d transition ; No JTD
F = [Cu (H2O)6]2+ ; Cu+2 → d9 → d-d transition ; has JTD
G = [Cu (en)2 (H2O)2]2+ ; Cu+2 → d9 → d-d transition ; has different ligand
H = [Co Cl3Br]2- ; Co+2 → d7 (high spin) → d-d transition ; has different ligand
A (Charge transfer) > D , H (tetrahedral) > E , F , G (octahedral) > B (d5 (high

spin )tetrahedral ) > C (d5 (high spin )octahedral )

A (Charge transfer) > H (tetrahedral + different ligand) > D (tetrahedral) > G
(octahedral + different ligand) > F (octahedral + JTD) > G (octahedral ; no JTD) >
B (d5 (high spin )tetrahedral ) > C (d5 (high spin )octahedral )
Answer - A > H > D > G > F > G > B > C
WHICH TRANSITION AND WHERE TO WHERE ?

CdS ; MnO4- ; TcO4- ; CrO4- ; Ni(CO)4
CdS – d10 (π-donor) LMCT
MnO4- ; TcO4- ; CrO4- :- d0 ; LMCT
Ni(CO)4 :- d10 converted ; MLCT (π-acceptor)
• Charge transfer : LMCT /MLCT /LLCT > MMCT
We cannot compare LMCT , MLCT , LLCT
• Among LMCT; we can compare ; similarly with MLCT and LLCT
• LMCT 2 type ka hota hai
1. p → s
2. p → d
Agar p → s k 2-3 example ho toh compare kr sakte hai
Agar p → d k 2-3 example ho toh compare kr sakte hai
But p → s wale ko p → d wale se compare nhi kr sakte hai
• LMCT – d0 → p → d
• LMCT – d10 → p → s
• MLCT – d10 → d → p
• Ligand ka orbital ; p – orbital hai
INTENSITY COMPARISON IN LMCT

• p→d LMCT
• Example:- KMnO4 , CrO42- ; VO43- ; TiO4- ; ScO45- ; :- all d0 ; LMCT
• All are tetrahedral, hybridisation of compounds is sd
• O is a weak π-donor. Electron will transfer from p-orbital to d-orbital of metal
• Sc3+ ; Ti4+ ; V5+ ; Cr6+ ; Mn7+ ; oxidation state increases ; intensity increases
•

2p and 3d have fixed energies, but we know as oxidation state increases ; splitting
increases and gap between 2p and e of 3d metal decreases. Thus electron will
transfer more and more from 2p to 3d , intensity increases
• Order of intensity:- KMnO4 > CrO42- > VO43- > TiO4- > ScO45-
• Gate 2011 – sabse kum wavelength ki energy kisme use hogi
• CrO42- ; MnO4- , TiO44- ; VO43- ;
• Cr+6 ; Mn+7 ; Ti+4 ; V+5
• Size - Mn+7 < Cr+6 < V+5 < Ti+4
• Jaha M-L bond length sabse kum hogi; waha pr sabse kum energy chahiye ; Ti+4
mei we need more energy and therefore we need shortest wavelength
• Ques. MnO4- , TcO4- ; ReO4- ; more intense ?

• Mn+7 ; Tc+7 ; Re+7
• 3d 4d 5d ; answer (a) MnO4-
• ReO4- is colourless ; MnO4- > TcO4- > ReO4-
• Almost all 5d metal complexes are colourless
• p-d transition depends upon metal orbital splitting (major factor)

❑ p→s LMCT
• L (π-donor) (p) → metal(s)
• Metal s mei electron tb lega jb d filled hoga ; therefore, d10
• d0 wale tetrahedral ki splitting se dekhte hai
• d10 wale octahedral ki splitting se dekhte hai
• d10 hai – no effect on splitting; here ligand is changed
• Comparison is asked between CdCl2/ CdBr2/ CdI2
• Comparison is asked between CdO/ CdS/ CdSe
• Order of intensity = CdO < CdS < CdSe
• Order of intensity = CdCl2< CdBr2< CdI2

• Shortest wavelength kon absorb krega ? CdSe or CdS
Answer. CdS kuki energy jyada hai ; wavelength short hai
• Compare the intensity of PbS and PbO

• Answer- PbO < PbS
SPECTRA
p2 k 15 microstates hote hai ; microstates ko further terms mei divide karte hai ; hrr
ek ek term or term symbol mei todte hai

❑ TERM
• Spin-spin coupling
• Orbital-orbital coupling
(inn dono k basis pr term nikaalenge)
❑ TERM SYMBOL is based on
• Spin-spin coupling
• Orbital-orbital coupling
• Spin-orbital coupling
MICROSTATES – ways of filling electrons in orbital

Microstates ko hum teen ways mei nikaal sakte h ; by elecronic configuration ; by
term ; by term symbol
• MICROSTATES BY ELECTRONIC CONFIGURATION
1. Agar valence shell 1 ho ; e.g. p2
2. Agar valence shell 1 se jyada ho ; e.g. p1s1
𝒏!
Number of microstates =
𝒓! 𝒏−𝒓 !
n=kitne electron maximum bhare jaa sakte hai
r= kitne electron bhare hue hai
➢ d4
𝑛! 10! 10! 10×9×8×7

Number of microstates = = = = = 210
𝑟! 𝑛−𝑟 ! 4! 10−4 ! 4!6! 4×3×2

• d5 s 1
• Number of microstates = nCr × mCx

10! 2! 10! 2!
• Number of microstates = × = ×
5! 10−5 ! 1! 2−1 ! 5!5! 1!1!
10×9×8×7×6
• Number of microstates = × 2 = 18 × 14 × 2 = 504
5×4×3×2
• d1
𝑛! 10! 10! 10
• Number of microstates = = = = = 10
𝑟! 𝑛−𝑟 ! 1! 10−1 ! 1!9! 1

• d2
𝑛! 10! 10! 10×9

𝑟! 𝑛−𝑟 ! 2! 10−2 ! 2!8! 2
• d3
𝑛! 10! 10! 10×9×8

𝑟! 𝑛−𝑟 ! 3! 10−3 ! 3!7! 3×2
• d4
𝑛! 10! 10! 10×9×8×7

𝑟! 𝑛−𝑟 ! 4! 10−4 ! 4!6! 4×3×2

• d5
𝑛! 10! 10! 10×9×8×7×6

𝑟! 𝑛−𝑟 ! 5! 10−5 ! 5!5! 5×4×3×2
• d6
𝑛! 10! 10! 10×9×8×7

𝑟! 𝑛−𝑟 ! 6! 10−6 ! 6!4! 4×3×2
• d7
𝑛! 10! 10! 10×9×8

𝑟! 𝑛−𝑟 ! 7! 10−7 ! 7!3! 3×2

• d8
𝑛! 10! 10! 10×9

𝑟! 𝑛−𝑟 ! 8! 10−8 ! 8!2! 2
• d9
𝑛! 10! 10! 10
𝑟! 𝑛−𝑟 ! 9! 10−9 ! 9!1! 1
• d10
𝑛! 10! 10! 10
• Number of microstates = = = = =1
𝑟! 𝑛−𝑟 ! 10! 10−10 ! 10!0! 1×10

Microstates of carbon in first excited state
C →2s1 2p3
• Number of microstates = nCr × mCx

2! 6! 2! 6!
• Number of microstates = × = ×
1! 2−1 ! 3! 6−3 ! 1!1! 3!3!
6×5×4
• Number of microstates = × 2 = 40
3×2
We can find ground state terms only and possible term symbols are studies only for
2 electron systems because we are studying in vectors and we can find vector
resultant of only two vectors like p2 ,d2, and f2
Jyada se jyada first excited state mei bta sakte hai

❑ TERM – coupling due to electron-electron repulsion
• Spin-spin coupling – S
• Orbital – orbital coupling – L
• Term = 2S+1L
• 2S+1 is called spin multiplicity
• L is called orbital-orbital coupling or resultant angular momentum
• S = s1 + s2 + s3 + …+ sn
• L = l1 + l2 + l3 + …+ ln
L 0 1 2 3 4
S P D F G

• p1
• L=1 → P
1
• s = ½ ; 2S+1 = 2 × + 1 = 2 ; term = 2P
2
• d1
• L=2 → D
1
• s = ½ ; 2S+1 = 2 × + 1 = 2 ; term = 2D
2

❖ Term of first excited state of carbon
❖ 2s2 2p2→ 2s1 2p3
❖ L=0→ S
❖ s = 4/2 = 2 ; 2S+1 = 5
❖ 5S
❖ Term of first excited state of beryllium

❖ 2s2 2p0→ 2s1 2p1
❖ L=1→ P
❖ s = ½+½ = 1 ; 2S+1 = 3
❖ 3P

Term No. of microstates
d1 d9 2D 10
d2 d8 3F 45
d3 d7 4F 120
d4 d6 5D 210
➢ d1
• L=2 → D
1
• s = ½ ; 2S+1 = 2 × + 1 = 2 ; term = 2D
2
➢ d2
• L=3 → F
• s = ½+½=1 ; 2S+1 = 2 × 1 + 1 = 3 ; term = 3F
➢ d3
• L=3 → F
3
• s = 3/2 ; 2S+1 = 2 × + 1 = 4 ; term = 4F
2
➢ d4
• L=2 → D
4
• s = 4/2 = 2 ; 2S+1 = 2 × + 1 = 5 ; term = 5D
2
➢ d5
• L=0 → S
5
• s = 5/2 ; 2S+1 = 2 × + 1 = 6 ; term = 6S
2
➢ d6
• L=5-3=2 → D
4
• s = 4/2 = 2 ; 2S+1 = 2 × + 1 = 5 ; term = 5D
2
➢ d7
• L=3 → F
3
• s = 3/2 ; 2S+1 = 2 × + 1 = 4 ; term = 4F
2
➢ d8
• L=3 → F
• s = ½+½=1 ; 2S+1 = 2 × 1 + 1 = 3 ; term = 3F

➢ d9
• L=2 → D
1
• s = ½ ; 2S+1 = 2 × + 1 = 2 ; term = 2D
2
➢ d10
• L=0 → S
• s = 0 ; 2S+1 = 2 × 0 + 1 = 1 ; term = 1S

d2 system
Ground state term
L=3→F
S = 2/2 ; 2S+1 = 3 ; 3F
Possible term symbol for 2 electron system
2S+1 = 3
(triplet)
2S+1=1
(singlet)
2 electron system can be triplet or singlet only
For example , for d3
S = 3/2 , ½, -1/2 , -3/2

2S+1 = 4 , 2
In 3 electron system we can get doublet or quartet only

➢ Key points for any 2 electron system in same orbital
• When L value is maximum (4) we have singlet state
• Spin will be triplet or singlet
Possible term symbol for f2 system

𝑛! 14! 14! 14×13
• f 2 – Number of microstates = = = = = 91
𝑟! 𝑛−𝑟 ! 2! 14−2 ! 2!12! 2
• Number of microstate from TERM
• Number of microstate = (2S+1)(2L+1)
• 1I = (1)(2×6+1) = 1×13 = 13
• 3H = (3)(2×5+1) = 3×11 = 33
• 1G = (1)(2×4+1) = 1×9 = 9
• 3F = (3)(2×3+1) = 3×7 = 21
• 1D = (1)(2×2+1) = 1×5 = 5
• 3P = (3)(2×1+1) = 3×3 = 9
• 1S = (1)(2×0+1) = 1×1 = 1
• 13 + 33 + 9 + 21 + 5 + 9 + 1 = 91

𝑛! 10! 10! 10×9
• d2 – Number of microstates = = = = =45
𝑟! 𝑛−𝑟 ! 2! 10−2 ! 2!8! 2
• Number of microstate = (2S+1)(2L+1)

• 1G = (1)(2×4+1) = 1×9 = 9
• 3F = (3)(2×3+1) = 3×7 = 21
• 1D = (1)(2×2+1) = 1×5 = 5
• 3P = (3)(2×1+1) = 3×3 = 9
• 1S = (1)(2×0+1) = 1×1 = 1
• 9 + 21 + 5 + 9 + 1 = 45
• Electron in different orbital ka ground state term

• Gate ka favorite – d5s1 and d5 ka aaya hua hai
L = +2+1+0-1-2-0=0 →S
S= 6/2 = 3
2S+1 = 7→7S
p1 d1
L = +2+1=3 →F
S= 2/2 =1
2S+1 = 3→3F
Ground state term
2 electron in different orbital – possible term
Maximum L value = 3
2 electron ka singlet ya triplet hi mil sakta hai
Here, when L value is maximum – S = ½ + ½ = 1 ; 2S+1 = 3 triplet
L = 3 ; S = ½ - ½ = 0 ; 2S+1 =1 singlet
When L is maximum , we get triplet as well as singlet
Possible L and S values
L = |l1+l2|, ………. |l1-l2|
S = |s1+s2|, ………. |s1-s2|
Here L = |1+2|, ………. |1-2|= 3,2,1 ; F,D,P
S = |1/2+1/2|, ………. |1/2-1/2|=1,0 ; 2S+1 = 3,1
Question – How many microstates for p1d1 when spin is not zero
Answer – 45
𝑛! 6! 6! 6×5
p2 – Number of microstates = = = = =15
𝑟! 𝑛−𝑟 ! 2! 6−2 ! 2!4! 2
• 1D = (1)(2×2+1) = 1×5 = 5
• 3P = (3)(2×1+1) = 3×3 = 9
• 1S = (1)(2×0+1) = 1×1 = 1
• 5 + 9 + 1 = 15

Term se 2 cheeze nikalte hai ; term symbol and mullkien symbol
• Term symbol (for free metal ion ) – energy and magnetism study krte hai
• Muliken symbol (for complex) – spectra study krne mei use hota h
• TERM SYMBOL – general formula 2S+1LJ

• Number of microstates = 2J+1
• Yaha extra coupling hoti hai
1. Russel sander coupling (L-S coupling)
2. J-J coupling (after atomic number = 30) g is also used here
J=|L+S|, ……….., |L-S|
Possible J values for 3P
J = |1+1|, ….,|1-1| = 2,1,0
3P
2 , 3P1 , 3P0 – TERM SYMBOLS
Question. Possible J values for 3D

3=2S+1 ; S = 1 ; L = 2
J = |2+1|,……,|2-1| = 3,2,1
3D , 3D , 3D – TERM SYMBOLS
3 2 1
Question. Possible J values for 3F

3=2S+1 ; S = 1 ; L = 3
J = |3+1|,……,|3-1| = 4,3,2
3F , 3F , 3F – TERM SYMBOLS
4 3 2

f2 ;1I ; S=0 ; L = 6 ; J = 6 ; 1I
6 (2×6+1) = 13
3H ; S=1 ; L = 5 ; J = 6, 5, 4 ; 3H (2×6+1) = 13
6
3H (2×5+1) = 11 33
5
3H (2×4+1) = 9
4
1G ; S=0 ; L = 4 ; J = 4 ; 1G (2×4+1) = 9
4
3F ; S=1 ; L = 3 ; J = 4, 3, 2 ; 3G (2×4+1) = 9
4
3G
3 (2×3+1) = 7 21
3G (2×2+1) = 5
2
1D ; S=0 ; L = 2 ; J = 2 ; 1D (2×2+1) = 5
2
3P ; S=1 ; L = 1 ; J = 2, 1, 0 ; 3P (2×2+1) = 5
2
3P
1 (2×1+1) = 3 9
3P (2×0+1) = 1
0
1S ; S=0 ; L = 0 ; J = 0 ; 1S (2×0+1) = 1
0
13 + 33 + 9 + 21 + 5 + 9 +1 = 91
d2
1G ; S=0 ; L = 4 ; J = 4 ; 1G (2×4+1) = 9
4
3F ; S=1 ; L = 3 ; J = 4, 3, 2 ; 3G (2×4+1) = 9
4
3G
3 (2×3+1) = 7
3G (2×2+1) = 5
2
1D ; S=0 ; L = 2 ; J = 2 ; 1D (2×2+1) = 5
2
3P ; S=1 ; L = 1 ; J = 2, 1, 0 ; 3P (2×2+1) = 5
2
3P
1 (2×1+1) = 3
3P (2×0+1) = 1
0
1S; S=0 ; L = 0 ; J = 0 ; 1S (2×0+1) = 1
0
9+9+7+5+5+5+3+1+1 = 45
p2
1D ; S=0 ; L = 2 ; J = 2 ; 1D (2×2+1) = 5
2
3P ; S=1 ; L = 1 ; J = 2, 1, 0 ; 3P (2×2+1) = 5
2
3P
1 (2×1+1) = 3
3P (2×0+1) = 1
0
1S ; S=0 ; L = 0 ; J = 0 ; 1S (2×0+1) = 1
0
5+5+3+1+1 = 15

d 2 – ground state term

Possible terms – 1G, 3F, 1D, 3P, 1S
Ground state term –
• Spin multiplicity should be high ; 3F or 3P
• L value should be maximum – 3 F is the ground state term
f2 – ground state term
Possible terms – 1I,3H,1G, 3F, 1D, 3P, 1S
Ground state term – 3H
• Which term is ground state ? 1G, 3F, 3D, 1P, 1S
• Answer – 3F

Which term symbol is ground state term symbol among 3F4, 3F3, 3F2,
Question is incomplete without electronic configuration
For ground state ,
|L+S| - for more than half filled
|L-S| - For less than half filled
Term
d1 d9 2D
d2 d8 3F
d3 d7 4F
d4 d6 5D
d2 and d8 – 3F ; |L+S| = 1+3 = 4 3F4 for d8

|L-S| = 1-3 = 2 3F2 for d2
1 1 5 3
d1 2D 2+ ……… 2 − ⇒ , ⇒ 2D3 Τ
2 2 2 2 2
d2 3F 3 + 1 ……… 3 − 1 ⇒ 4,3,2 ⇒ 3F2

3 3 9 7 5 3
d3 4F 3+ ……… 3 − ⇒ , , , ⇒ 4 F3 Τ
2 2 2 2 2 2 2
d4 5D 2 + 2 ……… 2 − 2 ⇒ 4,3,2,1,0 ⇒ 5D0

5 5 5
d5 6S 0+ ……… 0 − ⇒ ⇒ 6 S5 Τ
2 2 2 2
d6 5D 2 + 2 ……… 2 − 2 ⇒ 4,3,2,1,0 ⇒ 5D4

3 3 9 7 5 3
d7 4F 3+ ……… 3 − ⇒ , , , ⇒ 4 F9 Τ
2 2 2 2 2 2 2
d8 3F 3 + 1 ……… 3 − 1 ⇒ 4,3,2 ⇒ 3F4

1 1 5 3
d9 2D 2+ ……… 2 − ⇒ , ⇒ 2D5 Τ
2 2 2 2 2
d10 1S 0 + 0 ……… 0 − 0 ⇒ 0 ⇒ 1S0

More coupling ; more interelectronic repulsion
Fully filled L = 0 ; S = 0 ; therefore, J = 0 all couplings are zero
Therefore, fully filled is most stable
Half filled , L = 0 , S ≠ 0 ; therefore, J = S ; no J-J coupling here
MULLIKEN SYMBOLS
Used in spectra
Based on geometry

Octahedral Tetrahedral
S A1 g A1
P T1g T1
D T1g , Eg T1 , E
F T1g, T2g , A2g T1, T2 , A2
G (DPS) T2g, Eg , T1g, A1g T2, E, T1, A1
H (DPP) T2g, Eg , T1g, T1g T2, E , T1, T1
Number of microstate = spin multiplicity × dimension

Dimension of A , B = 1
Dimension of E = 2
Dimension of T = 3
d2
1S →
1g→ 1×1 = 1
1A
1G → 1T g → 1×3 = 3
2
1Eg → 1×2 = 2 9
1T g → 1×3 = 3
1
1A g → 1×1 = 1 45
1
3P→ 3T g → 3×3 = 9
1
1D → 1T g → 1×3 = 3 5
2
1Eg → 1×2 = 2
3F → 3A g → 3×1 = 3
2
1T g → 1×3 = 3 21
1
3T g → 3×3 = 9
1
ORGEL DIAGRAM
• For high spin complexes
• Simple diagram, easy to understand
• Possible transitions of high intensity are studied
• ∆𝑆 = 0
TANABE SUGANO DIAGRAM

• For high spin as well as low spin complexes
• Very difficult to understand
• Not possible transitions of very low intensity are studied
• ∆𝑆 = 0
• ∆𝑆 ≠ 0 are also studied
TRANSITION IN ORGEL DIAGRAM
d1 d9 2D
d2 d8 3F ; 3P
d3 d7 4F ; 4P
d4 d6 5D
TRANSITION IN TANABE SUGANO DIAGRAM

Electron transition in d1 and d2
Hole transition in d9 and d8

Orgel diagram – UV spectra ka explanation for high spin complex why are we
studying UV? Because we want data or information about the valence shell
electron that can give us information about M-L bonding
• Orgel diagram gives us information about covalent and ionic character
• Orgel diagram is used to explain the intensity of colour
• Orgel diagram is used to calculate CFSE
• Magnetism is also defined by UV spectra
•

Term
d1 d9 2D
d2 d8 3F
d3 d7 4F
d4 d6 5D
d1 octahedral – 2D
Unsymmetrical to symmetrical – electron transfer

One transition T2g → Eg ; [0.6 + 0.4] ∆𝑜 = 1 ∆𝑜
• d9 octahedral – 2D
symmetrical to Unsymmetrical – hole transfer
One transition Eg→T2g ; [0.6 + 0.4] ∆𝑜 = 1 ∆𝑜

When JTD will be there in complex, number of transition will be three ; splitting
will be high and instead of broad band we get 3 peaks
Due to strong JTD

In d1 we get a
shoulder
• d4 octahedral –
symmetrical to Unsymmetrical – hole transfer
One hole transition Eg→T2g ; [0.6 + 0.4] ∆𝑜 = 1 ∆𝑜

• d6 octahedral
Unsymmetrical to symmetrical – hole transfer
One electron transition T2g→Eg ; [0.6 + 0.4] ∆𝑜 = 1 ∆𝑜

• d1→ 1 electron transition → 2T2g → 2Eg ; ∆𝑜
• d9→ 1 hole transition → 2Eg →2T2g ; ∆𝑜
• d4→ 1 hole transition → 5Eg→5T2g ; ∆𝑜
• d6→ 1 electron transition → 5T2g → 5Eg ; ∆𝑜
For tetrahedral
• d1→ 2D → 1 electron transition → 2E → 2T2 ; ∆𝑡
• d9→ 2D → 1 hole transition → 2T2 →2E ; ∆t
• d4→ 5D → 1 hole transition → 5T2→5E ; ∆t
• d6→ 5D → 1 electron transition → 5E → 5T2 ; ∆𝑡

d1 octahedral → T2g → Eg (only learn this)

❑ d2 (octahedral)
Rules –
1. Tb tak transition karvate rahenge jab tak neeche symmetrical na bane
2. Agar electrom kum transfer karne pade toh electron transfer ; agar kum hole
transfer karne pade toh hole transfer

Rule – same mullikan symbol will repel each other
Also known as NON-CROSSING RULE
Same mulliken symbol repel each ither and different mulliken symbols cross each
other
• [V(H2O)6]2+ → 2 peaks are observed

• Both transition
3T g (F) → 3T g(P)
1 1
3T g (F) → 3A g
1 2
Merge with each other and we get 2 peaks for [V(H2O)6]3+
If ligand is stronger than water , transition shift towards right of the cross point
If ligand is weaker than water , transition shift towards left of the cross point
• 𝜈1 = 3T1g (F) → 3T2g(F)
• 𝜈2 = 3T1g (F) → 3A2g
• 𝜈3 =3T1g (F) → 3T1g(P)
• 𝜈1< 𝜈2< 𝜈3
• The ligand is weak
• 𝜈1 = 3T1g (F) → 3T2g(F)
• 𝜈2 = 3T1g (F) → 3T1g(P)
• 𝜈3 =3T1g (F) →3A2g
• 𝜈1< 𝜈2< 𝜈3
• The ligand is strong
• If 𝜈1 = 10000 cm-1;𝜈2 = 12000 cm-1; 𝜈3 = 15000 cm-1

For weak ligand ; what will be the value of Δ𝑜 ?
𝜈1 = 3T1g (F) → 3T2g(F)≠ ∆𝑜
Because line of 3T1g (F) is not a straight line ; we have a repulsive parameter , x
𝜈1 = ∆𝑜 + x
Agar question mei kaha ho ki replsive parameter ko ignore kr do ; then𝜈1 = ∆𝑜
• 3A2g and 3T2g(F) have no repulsion and gap is ∆𝑜 {1.2∆𝑜 − 0.2 ∆𝑜 = ∆𝑜}
• 𝜈2 = 3T1g (F) → 3A2g
• 𝜈3 =3T1g (F) → 3T1g(P)
• 𝜈2 − 𝜈1 = ∆𝑜 ;
• ∆𝑜 = 12000 − 10000 = 2000cm-1
• 𝜈1 = ∆𝑜 + x ;
• x = 𝜈1 − ∆𝑜 = 10000 – 2000 = 8000 cm-1
• For strong ligand, gap between T2g and A2g
• 𝜈3 − 𝜈1 = ∆𝑜 ;
• ∆𝑜 = 15000 − 10000 = 5000cm-1

❑ Covalent character / ionic character
Nephelauxetic parameter / Nephelauxetic effect
When metal was in free ion, it was having more electron – electron repulsion ; so it
binds with ligand , interelectronic repulsion was reduced
Overlapping se interelectronic repulsion kum ho gya; covalent character badh gya

M – free ion → interelectronic repulsion = 1000
Jitni jyada repulsion ; utna jyada Nephelauxetic effect
F, I – overlapping jyada hai I mei ; Nephelauxetic effect more of I
Soft ligand is I ; Nephelauxetic effect is more because overlapping is more
M in complex – interelectronic repulsion – 900 (less overlap)
800 (more overlap)
𝑩 𝒄𝒐𝒎𝒑𝒍𝒆𝒙 800 900
Nephelauxetic parameter or ratio, 𝜷 = = 𝑜𝑟 = 0.8 or 0.9
𝑩 𝑭𝒓𝒆𝒆 𝒊𝒐𝒏 1000 1000
Nephelauxetic parameter for F is more than that of I

Nephelauxetic effect is more when covalent character is more ; overlapping is more
; I ka jyada hai ; F ka kum
Nephelauxetic ratio ; I ka kum hai ; F ka jyada
Covalent character = (𝟏 − 𝜷) × 𝟏𝟎𝟎

Covalent character = (1 − 0.9) × 100= 10% covalent character
Ionic character = 90 %

Rachah parameter = inter electronic repulsion parameter

B for free metal ion ; B’ for complex
nephelauxetic effect is generated either due to ligand or metal {explained on the
basis of HSAB theory}
Nephelauxetic series (when metal is same)
F- < H2O < NH3 < en < ox2-< NCS- < Cl- < CN- < Br- < I-
Maximum nephelauxetic if for I- ; most covalent character
Nephelauxetic series (when ligand is same)
Mn2+ < Ni2+ ≈ Co2+ < Mo2+ < Fe4+ <Fe3+ < Ir3+ <Co3+ < Mn4+
𝑩 𝒄𝒐𝒎𝒑𝒍𝒆𝒙 𝒓𝒂𝒄𝒂𝒉 𝒑𝒂𝒓𝒂𝒎𝒆𝒕𝒆𝒓 𝒇𝒐𝒓 𝒄𝒐𝒎𝒑𝒍𝒆𝒙
Nephelauxetic parameter, 𝜷 = =
𝑩 𝑭𝒓𝒆𝒆 𝒊𝒐𝒏 𝒓𝒂𝒄𝒉𝒂 𝒑𝒂𝒓𝒂𝒎𝒆𝒕𝒆𝒓 𝒇𝒐𝒓 𝒇𝒓𝒆𝒆 𝒊𝒐𝒏

15 B in orgel diagram – B is Bcomplex ; racah parameter for complex
For weak ligand than H2O

𝜈1 = Δ𝑜 + 𝑥
𝜈2 = 1.2 + 0.8 Δ𝑜 + 𝑥 = 2.0Δ𝑜 + 𝑥
𝜈3 = 15𝐵 + 0.8Δ𝑜 + 𝑥 + 𝑥
𝜈2 − 𝜈1 = Δ𝑜
2Δ𝑜 + 𝑥 − Δ𝑜 + 𝑥 = Δ𝑜

d8 and d3 octahedral – same diagram
𝜈1 = Δ𝑜
𝜈2 = 2.0Δ𝑜 + 𝑥
𝜈3 = 15𝐵 + 1.2Δ𝑜 + 𝑥

Ques. [CrF6]3- show 3 absorption band 14000 cm-1, 22000 cm-1, 34000 cm-1. Find
out Δ𝑜 in cm-1
Answer - Δ𝑜 = 14000 cm-1= 𝜈1
𝜈2=2.0Δ𝑜 + 𝑥 = 22000 cm-1
x = 2 × 14000 − 22000 = 28000 − 22000 = 6000 cm-1
𝜈3 = 15𝐵 + 1.2Δ𝑜 + 𝑥
15𝐵 = 34000 − 6000 − 16800
B = 736 cm-1
1267 – electronic transition
9483 – hole transition
15𝐵 = 𝜈2+𝜈3-3𝜈1

MAGNETISM
2 jagah magnetism padhte hai ; physics mei aur chemistry mei ; dono ka aapas mei
koi relation nhi hai
• Physics sirf solid state ko consider krte hai
• Chemistry mei hum free metal ion and complex metal ion ko alag study krte hai
• Magnetic properties – diamagnetic hai ya paramagnetic hai
❑ Diamagnetic
Apply external force – repelled by opposite spin electrons
Diamagnetism is due to pairedDr.electrons

Kuldeep Garg (KDSIR CLASS NOTES) 280
❑ Paramagnetic
Apply external field – all add up
Paramagnetism is due to orbital motion as well as spin motion
• Magnetic field is generated by vibrations od electrons due to electric field

Slope 1 = paramagnetic susceptibility
Slope 2 = diamagnetic susceptibility
8 paired electrons diamagnetism show karenge but 1 unpaired electron show Para
magnetism and compound becomes Para magnetic
JUNGLE MEI EK HI SHER KAAFI HAI
𝝌𝒎 = 𝝌𝒎 𝑷 − 𝝌𝒎 𝑫
𝜒𝑚 =Molar susceptibility
𝜒𝑚 𝑃 = molar paramagnetic susceptibility
𝜒𝑚 𝐷 = molar diamagnetic susceptibility
But 𝜒𝑚 𝑃 is neglected
𝜒𝑚 = 𝜒𝑚 𝑃 magnetic momenta

𝜒𝑚 𝑃 is defined by 2 laws
1. Curie law (only paramagnetic)
2. Curie weiss law
• Ferromagnetism
• Antiferromagnetism
• Ferrimagnetism
❑ Diamagnetism
It is temperature dependent
❑ Paramagnetism is possible because of two reasons
1. Orbital motion
2. Spin motion
This study is theoretical, we will study afterwards
Now we are studying experimental things – that comes under physics
Paramagnetic – 3 jagah divide kiya

1. Ferromagnetic
2. Anti ferromagnetic
3. Ferrimagnetic
These 3 terms are used only in solid state
Two people – alag-alag dance kr rhe hai ; door-door hai jab ; therefore gaseous
state mei electrons ko ek doosre se koi lena dena nhi hai ; but when they come
closer; they will dance according to each other ; ya dono same dance karenge ; ya
ek khada hoke dance karega aur doosra jameen pr let k

In solid state they show cooperative magnetism
These are known as cooperative paramagnetism or supportive paramagnetism

• Curie law for paramagnetism
𝜇𝑒𝑓𝑓2×𝑁𝐴2
• 𝜒𝑚 = ; 𝜒𝑚 is magnetic susceptibility = tendency to magnetise
3𝑅𝑇
• 𝜇𝑒𝑓𝑓 = 2.84 𝜒𝑚𝑇 𝐵. 𝑀.
1 𝑐 𝜇𝑒𝑓𝑓2×𝑁𝐴2
• 𝜒𝑚 ∝ ; 𝜒𝑚 = ; where c = curie constant ; c =
𝑇 𝑇 3𝑅
• As temperature increases ; 𝜒𝑚 decreases
1 𝑇
• = ; 𝜒𝑚T = c
𝜒𝑚 𝑐

Curie weiss law
𝑐
𝜒𝑚 =
𝑇−𝜃
If 𝜃 is positive; T decreases; 𝜒𝑚 increases ; ferromagnetic
If 𝜃 is negative; T increases; 𝜒𝑚 decreases ; anti ferromagnetic
Tc = curie temperature
Tn = neel temperature
For supportive paramagnetism
𝜇𝑒𝑓𝑓 = 2.84 𝜒𝑚(𝑇 − 𝜃) 𝐵. 𝑀.
Jis temperature pr ferromagnetic behave as paramagnetic – Tc
Jis temperature pr antiferromagnetic behave as paramagnetic - TN

Paramagnetism – randomness – entropy is high
Ferrimagnetism – no randomness – alignment – entropy is low
MAGNETISM IN CHEMISTRY
2 parts mei padhenge – orbital motion and spin motion
• ORBITAL MOTION – paired and unpaired electrons show orbital motion
• SPIN MOTION – paired electrons cancel spin motion of each other ; unpaired
electrons give spin motion
• Spin motion k liye ek electron ka unpaired hona jaroori hai … but orbital
motion k liye electron ka unpair hona jaroori nhi hai
• If compound mei sab electrons paired hai ; tb bhi paramagnetic susceptibilty
kuch mil rhi hai toh orbital motion ki wajah se mil rhi hogi

ORBITAL PARAMAGNETISM IS TEMPERATURE DEPENDENT
Eg. KMnO4 – show paramagnetism
Chemistry paramagnetism (when unpaired electron is present)
• Free metal ion
➢ Orbital motion – hoga
➢ Spin motion – hoga
Unmarried – awaaragardi hogi ; may be spin and orbital do coupling
• Complex ion
➢ Orbital motion – nhi hoga
➢ Spin motion – hoga
Married – awaaragardi nhi kr sakte ; orbitals are quenched
𝜇𝑆 = 𝑛(𝑛 + 2 ) 𝐵. 𝑀. - spin only magnetic momenta
Jb orbital quench ho gye ; toh spin only wale k equal aane chahiye ; but aisa nhi
hua ;
Therefore, there is some orbital contribution. But if there is no orbital contribution
still there is deviation in magnetic momenta . That will be due to first order
perturbation – LS coupling

❖ ORBITAL MOTION
𝜇𝐿 = 𝐿(𝐿 + 1)
❖ SPIN MOTION
𝜇𝑆 = 𝑛(𝑛 + 2 ) 𝐵. 𝑀.
𝜇𝑠 = 4𝑆(𝑆 + 1)𝐵. 𝑀.
• MAGNETIC MOMENTA IN FREE METAL ION
Either 𝜇𝑆 or 𝜇𝑆 + 𝐿 or 𝜇𝐿𝑆 = 𝜇𝑒𝑓𝑓𝑒𝑐𝑡𝑖𝑣𝑒
LS means LS coupling
Upto atomic number 30; LS coupling is neglected
Free metal ion having unpaired electron – two categories
• Upto atomic number = 30
No LS coupling ; 𝜇𝑠 = 4𝑆(𝑆 + 1)𝐵. 𝑀.
𝜇𝑒𝑓𝑓 = 4𝑆 𝑆 + 1 + 𝐿(𝐿 + 1)𝐵. 𝑀.
• Lanthanides
LS coupling hogi
𝜇𝑠 = 4𝑆(𝑆 + 1)𝐵. 𝑀.
𝜇𝑒𝑓𝑓 = 𝑔 𝐽(𝐽 + 1)𝐵. 𝑀. ; where g = linde factor ; J = LS coupling
• 𝜇𝑒𝑓𝑓 of Cr+2 in free metal ion

Atomic number is less than 30 ; 𝜇𝑒𝑓𝑓 = 4𝑆 𝑆 + 1 + 𝐿(𝐿 + 1)𝐵. 𝑀.

Cr+2 → d4 ; L =+2; S=2
𝜇𝑒𝑓𝑓 = 4𝑆 𝑆 + 1 + 𝐿(𝐿 + 1)
𝜇𝑒𝑓𝑓 = 4 × 2 2 + 1 + 2(2 + 1)
𝜇𝑒𝑓𝑓 = 8×3+2×3
𝜇𝑒𝑓𝑓 = 24 + 6 = 30
• 𝜇𝑒𝑓𝑓 of Co+2 in free metal ion
Atomic number is less than 30 ; 𝝁𝒆𝒇𝒇 = 𝟒𝑺 𝑺 + 𝟏 + 𝑳(𝑳 + 𝟏)𝑩. 𝑴.
Co+2 → d7 ; L =+3 ; S=3/2
3 3
𝜇𝑒𝑓𝑓 = 4× + 1 + 3(3 + 1)
2 2
𝜇𝑒𝑓𝑓 = 15 + 12 = 27
LANTHANOIDS
4f 5d 6s
57 La [Xe] 0 1 2
58 Ce [Xe] 1 1 2
59 Pr [Xe] 3 0 2
60 Nd [Xe] 4 0 2
61 Pm [Xe] 5 0 2
62 Sm [Xe] 6 0 2
63 Eu [Xe] 7 0 2
64 Gd [Xe] 7 1 2
65 Tb [Xe] 9 0 2
66 Dy [Xe] 10 0 2
4f 5d 6s
67 Ho [Xe] 11 0 2
68 Er [Xe] 12 0 2
69 Tm [Xe] 13 0 2
70 Yb [Xe] 14 0 2
71 Lu [Xe] 14 1 2
La Lu Ce Gd
Lalu se gadbad hui – d mei electron aayega ; otherwise nhi aayega
Generally lanthanides show +3 oxidation state
Ce+4,Eu+2,Tb+2,Yb+2
Term symbol of Nd+3
Nd → [Xe] 4f4 5d0 6s2 ; Nd+3→ f3
S=3/2 ; 2S+1 = 4 ; L = 6 → I ; term = 4I

J = L+S … L-S
J = 6+3/2 ….. 6 – 3/2 = 9/2 (Less than half filled hai kuki)
Term symbol = 4I9/2
𝝁𝒎𝒎 (for lanthanides) = g 𝑱(𝑱 + 𝟏)
𝑺 𝑺+𝟏 −𝑳 𝑳+𝟏 +𝑱(𝑱+𝟏)
Where 𝒈 = 𝟏 +
𝟐𝑱(𝑱+𝟏)
J = |L-S| for less than half filled
J = |L+S| for more than half filled
J = |S| for exactly half filled
g lies from 0.7 to 1.5
• Pm+3
Pm → [Xe] 4f5 5d0 6s2 ; Pm+3→ f4
S=4/2 ; 2S+1 = 5 ; L = 6 → I
J = L-S = 6 – 2 = 4
𝑆 𝑆+1 −𝐿 𝐿+1 +𝐽(𝐽+1)
𝑔 =1+
2𝐽(𝐽+1)
2 2+1 −6 6+1 +4(4+1) 6−42+20 16
𝑔 =1+ =1+ =1− = 1 − 0.4 = 0.6
2×4(4+1) 40 40

𝜇𝑒𝑓𝑓 = g 𝐽(𝐽 + 1) = 0.6 4(4 + 1) = 0.6 4 × 5 = 0.6 × 20
• Pr+3
Pr → [Xe] 4f3 5d0 6s2 ; Pr+3→ f2
S=2/2 ; 2S+1 = 3 ; L = 5
J = L-S = 5 – 1 = 4
𝑆 𝑆+1 −𝐿 𝐿+1 +𝐽(𝐽+1)
𝑔 =1+
2𝐽(𝐽+1)
1 1+1 −5 5+1 +4(4+1) 2−30+20 1
𝑔 =1+ =1+ = 1 − = 0.8
2×4(4+1) 40 5
𝜇𝑒𝑓𝑓 = g 𝐽(𝐽 + 1) = 0.8 4(4 + 1) = 0.8 4 × 5 = 0.8 × 20

• Tb+3
Pr → [Xe] 4f9 5d0 6s2 ; Pr+3→ f8
S=6/2 ; 2S+1 = 7 ; L = 3
J = L+S = 3 + 3 = 6
𝑆 𝑆+1 −𝐿 𝐿+1 +𝐽(𝐽+1)
𝑔 =1+
2𝐽(𝐽+1)
3 3+1 −3 3+1 +6(6+1) 12−12+42 1
𝑔 =1+ =1+ = 1 + = 1.5
2×6(6+1) 84 2
𝜇𝑒𝑓𝑓 = g 𝐽(𝐽 + 1) = 1.5 6(6 + 1) = 1.5 6 × 7 = 1.5 × 42

• Eu+3
Eu → [Xe] 4f7 5d0 6s2 ; Eu+3→ f6
S=3 ; 2S+1 = 7 ; L = 3
J = L-S = 3 - 3 = 0
𝜇𝑒𝑓𝑓 = g 𝐽(𝐽 + 1) = g 0(0 + 1) = 0
Therefore, with LS coupling, 𝜇𝑒𝑓𝑓 of Eu+3 is zero
Spin only magnetic momenta ; 𝜇𝑠 = 4𝑆(𝑆 + 1)𝐵. 𝑀.= 4 × 3(3 + 1)𝐵. 𝑀. = 4 3
If LS coupling is not mentioned , 𝜇𝑒𝑓𝑓 = 4 3

• MAGNETIC MOMENTA IN COMPLEX ION
When orbital of ligand overlap, orbital motion of
Metal orbitals is stopped.orbital quench ho jaate h
Spin only magnetic momenta padhne lge
𝜇𝑒𝑓𝑓 thoda bohat upar neeche mila spin only wale se
Thoda jyada aaya toh maan liya relaxation in
Orbital quenching and orbital has started contributing
Wherever there is orbital contribution , 𝜇𝑒𝑓𝑓 > 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦
Orbital contribution kaha hoga ?
Answer – jaha T2g ya T2 unsymmetrical hoga

Oh HIGH SPIN LOW SPIN Td HIGH SPIN
d1 𝑦𝑒𝑠 𝑦𝑒𝑠 d1 𝑛𝑜
d2 𝑦𝑒𝑠 𝑦𝑒𝑠 d2 𝑛𝑜
d3 𝑛𝑜 𝑛𝑜 d3 𝑦𝑒𝑠
d4 𝑛𝑜 𝑦𝑒𝑠 d4 𝑦𝑒𝑠
d5 𝑛𝑜 𝑦𝑒𝑠 d5 𝑛𝑜
d6 𝑦𝑒𝑠 𝑛𝑜 d6 𝑛𝑜
d7 𝑦𝑒𝑠 𝑛𝑜 d7 𝑛𝑜
d10 𝑛𝑜 𝑛𝑜 d10 𝑛𝑜
• Ni2+ → d8 ; 𝜇𝑒𝑓𝑓 > 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 ; T2g is symmetrical ; Reason ? L≠0
• Cr3+ → d3 ; 𝜇𝑒𝑓𝑓 < 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 ; T2g is unsymmetrical ; Reason ? L≠0
• d5 ; 𝜇𝑒𝑓𝑓 = 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 ; T2g is symmetrical ; Reason ? L=0
• Orbital contribution hai ; 𝜇𝑒𝑓𝑓 > 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦

• No orbital contribution; no LS coupling ; 𝜇𝑒𝑓𝑓 = 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦
• LS coupling hai ; FIRST ORDER PERTURBATION ;
𝜇𝑒𝑓𝑓 > 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 and 𝜇𝑒𝑓𝑓 < 𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 (use experimental formula)
𝛼𝜆
𝜇𝑒𝑓𝑓 = 𝜇𝑠 1 − 𝐵. 𝑀.
Δ
When there is no orbital contribution (i.e. T2g is not unsymmetrical) and 𝜇𝑒𝑓𝑓 =
𝜇𝑠𝑝𝑖𝑛 𝑜𝑛𝑙𝑦 ; then see LS coupling

𝜶𝝀
𝝁𝒆𝒇𝒇 = 𝝁𝒔 𝟏 − 𝑩. 𝑴.
𝜟
Where 𝜇𝑠 = spin only magnetic momenta
𝛼 = contributing factor
𝜆 = LS coupling constant energy
Δ = crystal field splitting energy
𝛼 depends upon ground state Mullikan symbol is A or E ; when T is ground state
mullikan symbol – orbital contribution hoga
Ques. A complex [CoLn]2+ where L is neutal monodentate weak ligand. We found

magnetic momenta of this complex is 4.5 B.M. But we are confused here are four
ligands or six ligands i.e. tetrahedral or octahedral

Co2+ → d7 ;
𝜇𝑒𝑓𝑓 =3.9; lekin question mei 4.5 diya hai ; orbital contribution octahedral mei ; n=6

Ques. 625 nm – absorption band
-625 cm-1 – LS coupling
Cu2+ → d9 octa ; ground state = E ; 𝛼 =2
1 107 −1
E= = = 16000𝑐𝑚
𝜆 625 𝑛𝑚
𝜇 = 1.73
𝛼𝜆 2×(−625)
𝜇𝑒𝑓𝑓 = 𝜇𝑠 1 − 𝐵. 𝑀. = 1.73 1 − 𝐵. 𝑀. = 1.86 𝐵𝑀
Δ 16000

TEMPERATURE DEPENDENT MAGNETISM IN COMPLEXES

[HIGH SPIN – LOW SPIN]
[Co(H2O)6]3+→ Co3+ made strong field compound bna water k saath
[Co(H2O)3Cl3]3+→ iski study ki
Temperature dependent study ki
At low temperature → low spin complex
At high temperature → high spin complex
HIGH SPIN – LOW SPIN EQUILLIBRIA
Compounds that show low spin high spin equilibrium are d6 octahedral and d8
(coordination number =4)
▪ d6
▪ d6 is found incoordination number 6
Example – 1. [Fe(CN)5 NH3]3-
2. [Fe(Phen)3 (NCS)2]
3. [Fe(X)2]
Where X =

• CROSSOVER POINT
• d8
• Sqaure planar geometry is in equilibrium with tetrahedral geometry
• d8 is found incoordination number 4
• [Ni (CN)4]2- square planar
• [Ni Cl4]2- tetrahedral
➢ [Ni (py)2Cl2]
• High temperature → tetrahedral → paramagnetic → only one isomer
• Low temperature → square planar → diamagnetic → two isomers – cis / trans

COORDINATION REACTION
MECHANISM
CLASS NOTES FOR CSIR-NET/GATE/IIT JAM/TIFR/BARC/GSI
By – Dr. KULDEEP GARG (KD

SIR)
For more notes follow my telegram channel- kuldeepgargchemistry

REACTION MECHANISM OF COORDINATION COMPLEX
We need basic tools for reaction mechanism.

Reaction mechanism mei jab hum substitution karte hai toh 3 types se krte h
1. Dissociative
2. Associative
3. Interchange
General graph
R = reactant
I = intermediate
P = product
Types of reaction
Stoichiometric reactions Intimate reaction

Thermodynamic potential energy Kinetic activation energy
Jb compoumd (*) marks pr hoga … tb uski kinetic stability dekhenge

Jb compound (–) marks pr hoga tb uski thermodynamic stability dekhenge
Neeche walo se thermodynamic k baare mei information milegi

Upar walo se kinetic k baare mei information milegi
Stability is of two types in reaction mechanism

1. Thermodynamic stability
2. Kinetic stability
There is no relation between thermodynamic and kinetic stability

What is stability ?
Suppose , two students se water mangaya … A ne kaha laa denge … give 100 rupees
B ne kaha 1 lakh dedo …
Sir ne A wale se manga liya … jis reaction mei hume km energy deni pde … usko
thermodynamic stable compound mil gya
A ne 100 rupe toh liye pr 5 years baad water laake diya … isko kinetic kehte hai
Koi compound bohat saari energy release krke bn toh gya … pr 1 second mei hi khatam
ho gya … half life time bohat kum tha … isko kinetic unstable kahenge
Bn toh gya … but uski age kya hai …
• Koi compound jyada energy release krke bna … aur half life time bhi acha hai … this
is known as thermodynamic stable and kinetic stable
• Koi compound jyada energy release krke bna … aur half life time kum hai … this is
known as thermodynamic stable and kinetic unstable
• Koi compound kum energy release krke bna … aur half life time bhi acha hai … this
is known as thermodynamic unstable and kinetic stable
Thermodynamic stability
1. Stable – perfect
2. Unstable – imperfect
Kinetic stability
1. Stable – inert
2. Unstable – labile
Example - [Cu(H2O)6]2+ this is thermodynamically stable but highly inert

Studied in JTD
example - [Hg(CN)4]2+ this is thermodynamically stable but highly labile
Question poochne k tareeke se pta lg jayega ki konsi stabilty pooch rha h

Rate ki baat hogi toh kinetic wali pooch rhe h
General pooch rha h toh thermodynamic wali pooch rha hai
THERMODYNAMIC STABILITY
Jab hum reaction karvate hai … complex bnate hai … hum complex bnate nhi hai … substitution
krvate hai …
Metals are in aqueous solutions in original form … H2O decide karega ki metal ko jaane dega ya
nhi doosre ligand k saath …
Water ligand is replaced by other ligands
• M(H2O) complex + 100000 → M(L) … no reaction
Kabhi toh water ne kaha ki 1 lakh rupe do aur metal ko le jao … ligand ne kaha hume ni chahiye …
reaction nhi hui
• M(H2O) complex → M(L) + 100000… no reaction
Water ne ligand ko metal bhi de diya aur 10000 rupe bhi diye … reaction is possible
Jitna jyada formation constant hoga … utna jyaada M-L complex bn rha hoga ∆𝐺 = 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 -
energy is released that’s why product form ho rha hai …
• ∆𝑮 = −𝐑𝐓 𝐥𝐧𝐊 ;K = equilibrium constant
∆𝑮
• 𝒍𝒏𝑲 = −
𝑹𝑻
K jitna jyada , ∆𝐺 utna negative ; aur compound thermodynamically stable hoga

∆𝑮 = ∆𝑯 − 𝑻∆𝑺
∆𝐺 = 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 hone k liye ∆𝐻 = 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 and ∆𝑆 = 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒
▪ ∆𝑯 kaha kaha se nikal k aati hai
➢ CFSE – jitni jyada CFSE ; utni jyada thermodynamic stability
➢ JTD – JTSE mili ; type of enthalpy
➢ Metal ligand strength
➢ Z effective
▪ ∆𝑺 = 𝒑𝒐𝒔𝒊𝒕𝒊𝒗𝒆
➢ Chelation; jitna jyada chelation
▪ ∆𝑯 and ∆𝑺 both se related factors

➢ Macrocyclic ligand
➢ Resonance factor (aromatic ring)
➢ Clathrate factor (cryptands)

BASED ON EQUILIBRIUM CONSTANT
Formation of compound - types se hota h

➢ Stepwise formation ; k1; k2; k3; k4
➢ Overall formation ; 𝛽𝑛
➢ Overall 𝛽𝑛
[ML6]
M (aq) + L ML6 ; 𝛽𝑛 = 𝑀 𝐿 6
➢ Stepwise
𝑘1
[ML1]
M (aq) + L ML1 ; 𝑘1 = 𝑀 𝐿
𝑘2
[ML2]
ML1 + L ML2 ; 𝑘2 = 𝑀L1 𝐿
𝑘3 [ML3]
ML2 + L ML3 ; 𝑘3 =
𝑀L2 𝐿
𝑘4 [ML ]
ML3 + L ML4 ; 𝑘4 = 𝑀L 4𝐿
3
𝑘5 [ML ]
ML4 + L ML5 ; 𝑘5 = 𝑀L 5𝐿
4
𝑘6 [ML ]
ML5 + L ML6 ; 𝑘6 = 𝑀L 6𝐿
5
[ML ] [ML ] [ML ] [ML ]
𝛽3 = 𝑀 𝐿66 = 𝑀L 3𝐿 × 𝑀L 2𝐿 × 𝑀 𝐿1 = 𝑘3. 𝑘2. 𝑘1
2 1
𝛽3 = 𝑘3. 𝑘2. 𝑘1
𝛽𝑛 = 𝑘1. 𝑘2.𝑘3… 𝑘𝑛
Overall formation constant = multiplication of stepwise formation constant
∆𝐺 = −RT ln𝛽𝑛
Generally, 𝒌𝟏> 𝒌𝟐> 𝒌𝟑> 𝒌𝟒> 𝒌𝟓> 𝒌𝟔
Some cases are there ,where 𝑘1 is not the greatest
1. When compound changes its geometry … octahedral se tetrahedral mei change ho rha ho
2. When compound changes its spin … high spin se low spin mei convert ho rha ho
entropy
𝑘
Example – [Cd(H2O)6]2+ + Br- 1
[Cd(H2O)5Br]+ + H2O n = 0
[Cd(H2O)5Br]+ + Br- 𝑘2 [Cd(H2O)4Br2] + H2O n=0
[Cd(H2O)4Br2] + Br- 𝑘3 [Cd(H O) Br ]- + H O n=0
2 3 3 2
[Cd(H2O)3Br3]- + Br- 𝑘4 [CdBr4] 2- + 3H2O n=4–2=2
𝑘1> 𝑘2> 𝑘3< 𝑘4
This order can be explained on the basis of entropy
Jitne number of molecule badhenge utni entropy increase hogi
Fourth step mei entropy increase ho gyi … iss liye rate jyada ho gya
NOTE :
[Co(H2O)6]2+
[Ni(H2O)6]2+ + Cl / Br / I - octahedral se tetrahedral mei change hoga
[Cu(H2O)6]2+ 𝒌𝟏> 𝒌𝟐> 𝒌𝟑< 𝒌𝟒

Example –
𝑘1
2+
[Fe(H2O)6] + bpy [Fe(H2O)4bpy]2+ + 2 H2O
𝑘2
[Fe(H2O)4bpy]2+ + bpy [Fe(H2O)2(bpy)2]2+ + 2 H2O
[Fe(H2O)2(bpy)2]2+ + bpy 𝑘3 [Fe(bpy)3]2+ + 2 H2O
Order = 𝒌𝟏> 𝒌𝟐< 𝒌𝟑
[Fe(H2O)6]2+ - Fe2+ → d6 → high spin → CFSE = - 0.4 ∆𝑜

[Fe(bpy)3]2+ - Fe2+ → d6 → low spin → CFSE = - 2.4 ∆𝑜
Yaha humne enthalpy factor k basis pr explain kiya
High spin se low spin complex mei change ho gya … CFSE mei change aa gya …
rate of formation constant ka order change ho gya … general wala nhi aaya
FACTORS AFFECTING THE STABILITY OF COMPLEXES
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
ENTHALPY FACTORS , ∆𝐻 – Zeff ; CFSE ; JTD ; M-L strength ; - HSAB theory

; symbiosis theory
ENTROPY FACTORS , ∆𝑆 – chelation
ENTHALPY + ENTROPY FACTORS
Macrocyclic factors – 1. macrocyclic chelate ligand eg. EDTA

2. macrcyclic crown ether eg. 12-crown-4
Clathrates – eg. Cryptands
Resonance – eg. acac
COORDINATION CHEMISTRY LECTURE NO. 4 (RM)
Which compound is stable and why ?

O.S. ↑ ; CFSE ↑ ; Zeff ↑; Principle quantum number ↑ ; Zeff ↑
Question 1 – [Co(H2O)6]2+ and [Co(H2O)6]3+

Co2+ and Co3+ ; O.S. ↑ ; Zeff ↑; stability↑
[Co(H2O)6]2+ < [Co(H2O)6]3+
Question 2 – [Ni(H2O)6]2+ and [Cu(H2O)6]2+

Ni2+ (d8) and Cu2+ (d9) ;
[Ni(H2O)6]2+ < [Cu(H2O)6]2+
Left to right – Zeff increases ; d9 has JTD – MORE STABLE
NOTE : the above rule is valid only when monodentate ligand and EDTA are present
IRWIN WILLIAM SERIES (when O.S. is same and ligand is same)
Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+
Cu2+ is most stable ;
Irwin william series is for coordination number 6
In coordination number 4 ; [NiCl4]2- > [CuCl4]2-
Question 3 – [Ni(en)3]2+ and [Cu(en)3]2+

Ni2+ (d8) and Cu2+ (d9) ;
[Ni(en)3]2+ < [Cu(en)3]2+ by irvin william series
NOTE : Irwin william series is only for monodentate ligand and EDTA
en is a chelating ligand [Ni(en)3]2+ > [Cu(en)3]2+
Cu2+ (d9) has JTD
JTD ki wajah se strain ho jaata hai

Iss liye unstable

Question 4 – [Ni(en)2(H2O)2]2+ and [Cu(en)2(H2O)2]2+ both trans
[Cu(en)2(H2O)2]2+ > [Ni(en)2(H2O)2]2+

Easily bn sakta hai
Question 5 – [Ni(en)2(H2O)2]2+ and [Cu(en)2(H2O)2]2+ both Cis
[Cu(en)2(H2O)2]2+ < [Ni(en)2(H2O)2]2+
Unstable due to strain

ENTROPY FACTORS
1. [Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+ + 6H2O
2. [Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6H2O
Entropy in 1 = 7 – 7 = 0
Entropy in 2 = 7 – 4 = 3 ; ∆𝐺 = 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 ; 2>1
ENTHALPY FACTOR IN CHELATION (Minor factor)
M k upar 6 H2O hai … ek ek NH3 aayenge ; energy use hogi 6 NH3 lagne k liye
whereas jb en aayega ; ek jud gya agar H2O hata k … toh doosra toh khud hi jud
jayega … em energy lagani padegi …
STABILITY OF CHELATE RING

RESONANCE EFFECT
acac - acetoacetate

Question – [M(acac)3]
How many chelate rings ?
Ans. 1
Kitne member wali ring ?
Ans. 6
If they ask in unstable structure
Number of chelate ring = 2
Kitne membered ring = 4 membered
[Al(acac)3] , [Ti(acac)3] , [Cr(acac)3] , [Co(acac)3] all are stable due to resonance and 6 membered
chelate rings
B > A because B has resonance although A has 5 membered ring ; but resonance is absent
Question : which one is most stable
1. [Cd(H2O)4]2+ + 4 NH3 [Cd(NH3)4]2+ [I]
2. [Cd(H2O)4]2+ + 2 en [Cd(en)2]2+ [II]
3. [Cd(H2O)4]2+ + trien [Cd(trien)]2+ [III]
Answer. III > II > I
Entropy : 1. 5 – 5 = 0
2. 5 – 3 = 2
3. 5 – 2 = 3

METAL LIGAND STRENGTH
Acidity pooch sakte hai
Jitna jyada M aur O ka bond acha hoga
Utna jyada H bahar jaana chahega
Acidity increases
O.S. jyada ; acidity jyada; thermodynamic stability jyada
Ek p block wala liya aur ek d block wala liya … kiski acidity jyada hogi
[Al(H2O)6]3+ and [Fe(H2O)6]2+
Answer - Al3+ oxidation state jyada ; acidity jyada
Ab dono ka oxidation state bhi same ho jaye agar

[Al(H2O)6]3+ and [Fe(H2O)6]3+
Answer - [Fe(H2O)6]3+
d is prefered over p block ; when oxidation state is same
[Al(H2O)6]3+ , [Cr(H2O)6]3+ , [Fe(H2O)6]3+
Compare Fe and Cr on the basis of size ; size chota , acidit jyada
[Fe(H2O)6]3+ > [Cr(H2O)6]3+ > [Al(H2O)6]3+
MACROCYCLIC EFFECT
1. Chelating
I. [Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+
II. [Ni(H2O)6]2+ + 3 en [Ni(en)3]2+
III. [Ni(H2O)6]2+ + EDTA [Ni(EDTA)]2+
ENTROPY : III > II > I
Question:
A. [Cu(NH3)6]2+
B. [Cu(en)3]2+
C. [Cu(EDTA)]2+
Answer. C > A > B
C mei enthalpy is very high; C mei JTD hai , but ligand is macrocyclic and arrange

Karne mei energy nhi lgi
B is unstable due to JTD
en – 3 baar judega ; enthalpy jyada use hui
EDTA ek baar mei jud gya ; enthalpy kum use hui
❖ [Ni(en)3]2+ > [Cu(en)3]2+

❖ [Ni(EDTA)]2+ < [Cu(EDTA)]2+ … by irwin william series
❖ PORPHYRIN RING
For porphyrin ring
Ni2+ >Cu2+ > Co2+ > Fe2+ >Zn2+
For EDTA – irwin william series

❖ CRYPTANDS
➢ C – 211 → Li+
➢ C – 221 → Na+
➢ C – 222 → K+
➢ C – 322 → Rb+ / Cs +
➢ Cryptands mei 2 NITROGEN ; 211 ka mtlb 2 O ; 1 O ; 1 O

➢ Cryptands have fixed size of cage ; C – 211 fits Li+ ion and so on
❖ CROWN ETHER
➢ 12 crown 4 Li+
➢ 15 crown 5 Na+
➢ 18 crown 6 K+
➢ 21 crown 7 Rb+
➢ 24 crown 8 Cs+
KINETIC STABILITY
Compounds that were kinetically stable – Inert
Compounds that were kinetically unstable – Labile
➢ Labile will react fast; inert will react slow
➢ Labile complexes show dissociation reaction
➢ Inert complexes show association reaction
➢ Dissociation – seat khali kr k chala gya koi … aaram se beth jao
➢ Association – koi aaya … kisi doosre se jabardasti seat khali krvayi aur fir betha
➢ Dissociation is better than association.

➢ Half life time ; t1/2 > 1 minute – inert
➢ Half life time ; t1/2 < 1 minute – labile
➢ Half life time ; t1/2 = 1 minute – moderate – Ni
➢ On the basis of VBT

All outer sphere complexes are labile – sp3d2 ; Ni – moderate

Inner sphere orbital complexes having any low – lying empty d-orbital – labile
When checking labile and inert ; First check

1. Electronic configuration
2. Zeff
Question. [V(H2O)6]3+ and [V(H2O)6]2+

1. Which one is kinetic stabile ?
Ans. [V(H2O)6]3+ < [V(H2O)6]2+
2. Labile / inert
Ans. [V(H2O)6]3+ - labile; [V(H2O)6]2+ - inert
3. Water exchange reaction kon dega
Ans. [V(H2O)6]3+
4. Rate of substitution
Ans. [V(H2O)6]3+ > [V(H2O)6]2+ Dr. KULDEEP GARG
V3+ → d2 → d2sp2 → IOC → Labile
V3+ → d3 → d2sp2 → IOC → Inert

ORDER TO BE FOLLOWED
1. Electronic configuration
2. Zeff
a) Zeff ∝ O.S.
1
b) Zeff ∝
𝑠𝑖𝑧𝑒
Question. [V(H2O)6]2+ and [Cr(H2O)6]3+

V2+ → d3
Cr3+ → d3
O.S. → +3 > +2
[Cr(H2O)6]3+ is kinetically more stable
Question. [NiL6]2+ and [PtL6]2+

Ni2+ → d8
Pt2+ → d8
Electronic configuration is same ; Oxidation state is same ; Size – Pt > Ni
Yaha size nahi dekhenge … size hamesha left to right hi dekhna hai
3d
4d Zeff increase ; Pt > Ni (stability)
5d
Question. [Na(H2O)6]+ ; [Mg(H2O)6]2+; [Al(H2O)6]3+

Answer – oxidation state = Na+ < Mg2+ < Al3+
Order of lability : . [Na(H2O)6]+ > [Mg(H2O)6]2+> [Al(H2O)6]3+
Question. [Sr(H2O)6]2+ ; [Ca(H2O)6]2+; [Mg(H2O)6]2+

Fast reaction ?
[Sr(H2O)6]2+ > [Ca(H2O)6]2+> [Mg(H2O)6]2+
For alkali earth metals, Zeff decreases from up to down in s block
In p block ; top to bottom ; Zeff increases
Size bada – voh labile
Order of rate of water exchange reaction – Cu2+ > Cr2+ ; because Cu2+ has JTD – highly
unstable (kinetically)
Cu2+ > Cr2+ > Zn2+ > Mn2+ > Fe2+ > Co2+ > Ni2+ >V2+
Reason JTD oh mei nhi on the basis of size
1
jaana chahta rate ∝
𝑠𝑖𝑧𝑒
LABILE MODERATE INERT
Question
1. [Ti(H2O)6]3+ Ti3+ → d1 → Labile
2. [Fe(H2O)6]3+ Fe3+ → d5 → Labile
3. [V(H2O)6]3+ V3+ → d2 → Labile
4. [Cr(H2O)6]3+ Cr3+ → d3 → inert
Question – order of kinetic stability [V(H2O)6]2+ ;[Co(H2O)6]2+ ;[Cr(H2O)6]3+

GATE 2018
1. [V(H2O)6]2+ V2+ → d3 → INERT ; O.S. is less
2. [Co(H2O)6]2+ Co2+ → d7 → Labile
3. [Cr(H2O)6]3+ Cr3+ → d3 → inert ; O.S. is more
[Cr(H2O)6]3+ > [V(H2O)6]2+ > [Co(H2O)6]2+
Dr. KULDEEP GARG

COORDINATION CHEMISTRY LECTURE NO. 5 (RM)
On the basis of VBT ; Labile and inert

1. Hybridisation – sp3d2 – always labile
2. Low lying vacant d orbitals in d2sp3 hybridisation
3. Charge – charge is more – inert
1
4. Zeff ∝ inertness ; Zeff ∝ oxidation state ; Zeff ∝ 𝑠𝑖𝑧𝑒
Which complex is more stable [V(H2O)6]2+ and [V(H2O)6]3+

[V(H2O)6]2+ V2+ → d3 → INERT
[V(H2O)6]3+ V3+ → d2 → labile
[V(H2O)6]2+ is more stable
Question – order of rate of reaction

[Al F6]3- ; [Si F6]2- ; [P F6]- ; [S F6]
Answer – Al3+ ; Si4+ ; P+5 ; S+6
Left to right ; Zeff increases as charge increases
[Al F6]3- > [Si F6]2- > [P F6]- > [S F6]
Labile inert
Question – order of lability

Cr3+ ; Al3+ ; Cr2+ ; Ni2+
Answer –
1. Cr3+ → d3 → INERT
2. Cr2+ → d4 → labile
3. Ni2+ → d8 → labile (moderate)
Cr2+ >Ni2+ > Al3+ > Cr3+
Inertness dekhte hue , transition metal and non transition metal ko jab compare karte hai ;
pehle charge dekho ; charge jyada – inert ; if charge is same ; give priority to d- block – d
block wala jyada inert
ON THE BASIS OF CFT
Reaction mechanism
If CFSE of substrate is less and CFSE of intermediate is more ; the substrate is called labile
Bodse and Pearson gave an experimental table
Difference between CFSE of intermediate and substrate
CFSE of I = -2.0 ; CFSE of substrate = -1.2 ;
Intermediate ki CFSE – substrate ki CFSE = -2.0 – (-1.2 ) = - 0.8 (agar negative hoga toh labile)
In some books ; substrate – intermediate = -1.2 – (-2.0) = + 0.8

We are studying , substrate – intermediate
For labile ; positive
For inert ; negative
High spin High spin Low spin Low spin
Systems C.NO. = 5 C.NO. = 7 C.NO. = 5 C.NO. = 7
d0 0 0 0 0
d1 +0.57 +1.28 +0.57 +1.28
d2 +1.14 +2.56 +1.14 +2.56
d3 -2.00 -4.26 -2.00 -4.26
d4 +3.14 -1.70 -1.43 -2.98
d5 0 0 -0.86 -1.70
d6 +0.57 +1.28 -4.00 -8.52
d7 +1.14 +2.56 +1.14 -5.34
d8 -2.00 -4.26 -2.00 -4.26
d9 +3.14 -1.70 +3.14 -1.07
d10 0 0 0 0
Coordination number – 5
d1, d2 → high/low spin → labile
d3 → high/low spin → inert
d7, d9 → high/low spin → labile
d8 → high/low spin → inert
d4 → high spin → labile
d4 → low spin → inert
d5 → low spin → inert
d6 → low spin → highly inert
LABILE - d1, d2 ; d7, d9 ; d4 → high spin ; d6 → high spin

INERT - d3, d8 , d4 → low spin ; d5 → low spin ; d6 → low spin
REACTION MECHANISM
3 routes hote hai
1. Dissociative mechanism → dissociation activation (Dd)
2. Association mechanism → association activation (Aa)
3. Interchange mechanism → associative activation (Ia)
→ dissociative activation (Id)
Ia – I denotes the type of mechanism and jo subscript mei likha hai voh batata hai ki kis
type ka activation hai
Reaction ko 2 methods se padh sakte hai

➢ Stoichiometric calculations
o Thermodynamic stability
o Minima of curve
➢ Intimation calculations
o Kinetic stability
o Maxima of curve
DISSOCIATIVE
ML6 −𝐿 ML5 +𝑌 ML5Y

𝑠𝑙𝑜𝑤 intermediate
Jab L alag ho rha hai voh step humara rate determining step hai ; that is Dd (dissociative mechanism
with dissociation activation)
And jis step mei Y add ho rha hai voh humara Da (dissociative mechanism with association
activation) wala step hai
ASSOCIATIVE
ML6 +𝑌 ML6Y −𝐿 ML5Y

𝑠𝑙𝑜𝑤 intermediate
jis step mei Y add ho rha hai voh step humara rate determining step hai ; that is Aa (associative
mechanism with association activation)
And jab L alag ho rha hai voh humara Ad (associative mechanism with dissociation activation) wala
step hai

INTERCHANGE
+𝑌
ML6 Y---- ML5----L MYL5
𝐼𝑎
Transition state
Pehle Y judne laga
+𝑌
ML6 L---- ML5----Y ML5Y
𝐼𝑑
Pehle L tootne laga
In interchange mechanism ,
no intermediate is formed only a transition state is generated

LIGANDS
Ligands two types k hote hai
1. Auxiliary ligand or spectator ligand
➢ Trans auxiliary ligand (TAL) – 1800 to the leaving ligand
➢ Cis auxiliary ligand (CAL) – 900 to the leaving group
2. Leaving ligand
TAL k case mei hum electronic factors dekhte hai
Agar TAL leaving ligand k saamne lga hota hai; aur agar voh pi donor ligand hai toh leaving
ligand easily remove ho jaata hai
Agar CAL is pi- donor ; no effect ; dz2 mei electron hi nhi aaye

CAL k case mei sterric factor dekhte hai ;
Agar cis position pr big groups lg jayenge to leaving ligand ko nikalna hi padega
Sterric factor ka TAL k liye koi effect nhi hoga kuki voh door ho jaata hai
DISSOCIATIVE MECHANISM
ML5
square pyramidal +𝑌
ML6 ML5Y
ML7
trigonal bipyramidal +𝑌
KINETICS OF DISSOCIATIVE MECHANISM
Rate kya hoga ?

𝑘1𝑘3 𝑀𝐿5𝑋 [𝑌]
a) 𝑘2 𝑋 +𝑘3[𝑌]
b) 𝑘1 𝑀𝐿5𝑋
c) 𝑘2 𝑋
Answer : (a)
𝑘1
ML5X ML5 + X {fast}
𝑘2
ML5 + Y 𝑘3 ML5Y {slow}
Rate = k3 [ML5][Y]
On applying SSA on [ML5]
𝑑[ML5]
= 0 = k1 [ML5X] – k2 [ML5][X] – k3 [ML5][Y]
𝑑𝑡

k1 [ML5X] = k2 [ML5][X] + k3 [ML5][Y]
k1 [ML5X] = {k2 [X] + k3 [Y] } [ML5]
𝑘1 𝑀𝐿5𝑋
[ML5] =
𝑘2 𝑋 +𝑘3[𝑌]
Rate = k3 [ML5][Y]
𝒌𝟏𝒌𝟑 𝑴𝑳𝟓𝑿 [𝒀]
Rate = 𝒌𝟐 𝑿 +𝒌𝟑[𝒀]
When [Y] is high ; k3[Y] >>> k2 [X]

Rate = 𝑘3[𝑌]
= 𝑘1 𝑀𝐿5𝑋
When [X] is high; k2 [X] >>> k3[Y]

𝑘1𝑘3 𝑀𝐿5𝑋 [𝑌] 𝑘1𝑘3 𝑀𝐿5𝑋 [𝑌] 𝑘𝑜𝑏𝑠 𝑀𝐿5𝑋 [𝑌]
Rate = = =
𝑘2 𝑋 𝑘2 𝑋 𝑋
𝑘𝑘
Where kobs = 1 3
𝑘2
COORDINATION CHEMISTRY LECTURE NO. 6 (rm)
[ML5X] +𝑌 [ML5Y]
When Y = NO2 ; I ; Br ; Cl ; F – rate is almost same
Rate is not depending on the concentration of [Y]
We can say that the reaction is SN1 because molecularity is 1
Ligands 2 type k hai ; TAL and CAL

TAL k case mei electronic factor dekhne hai
CAL k case mei sterric factor dekhne hai
1 1
1. Zeff ∝ O.S. ; Rate ∝ 𝑍𝑒𝑓𝑓
∝ 𝑂.𝑆.
2. M-X bond strength jyada hogi toh rate less hoga ; X = leaving ligand
1
Rate ∝
𝑀𝑋 𝑏𝑜𝑛𝑑 𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ
Question. [ML5X]2+ ; [ML5X] 3+ ; [ML5X] 4+

1
Answer - Rate ∝ 𝑂.𝑆. M2+ > M3+ > M4+
3. JTD
[Cu(H2O)6]2+ ; [Ni(H2O)6]2+
k1 k2
k1 > k2 because of JTD Lability increase
4. Nature of leaving group

Jitna acha leaving group hoga ; utna jaldi leave karega ; rate increase ho jega
[ML5F]2+ ; [ML5Cl]2+ ; [ML5Br]2+ ; [ML5I]2+ ;
Order of rate : [ML5F]2+< [ML5Cl]2+ < [ML5Br]2+ < [ML5I]2+
Effect of TAL and CAL
If TAL is a pi – donor ;
It increases electron density on metal
Then L leaves fastly
Rate is fast
Example – I. [ML4IX] X is a leaving group
II. [ML4FX] X is a leaving group
Both are trans
I is a better pi donor than F
Rate – I > II
If TAL is a good pi – acceptor ; electron density M pr kum ho gyi toh metal ligand se
electron leke strong bond banata hai
If TAL is pi-donor ; Rate ∝ pi- donor

𝟏
If TAL is pi- acceptor ; Rate ∝
𝒑𝒊 𝒂𝒄𝒄𝒆𝒑𝒕𝒐𝒓

SUMMARY
1
• Rate ∝
𝑍𝑒𝑓𝑓
1
• Rate ∝ 𝑂.𝑆.
1
• Rate ∝
𝑀𝑋 𝑏𝑜𝑛𝑑 𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ
• Rate ∝ JTD
1
• Rate ∝ 𝐶𝐹𝑆𝐸
Majorly on TAL
• Rate ∝ pi- donor
1
• Rate ∝
𝑝𝑖 𝑎𝑐𝑐𝑒𝑝𝑡𝑜𝑟
• Rate ∝ Steric crowding Dr. KULDEEP GARG
Question. [M(NH3)5X]2+ ; [M(NR2H)5X]2+ ; [M(NR3)5X]2+ ; [M(NRH2)5X]2+
Order of rate : [M(NR3)5X]2+ > [M(NR2H)5X]2+ > [M(NRH2)5X]2+ > [M(NH3)5X]2+
CHEMISTRY OF PHOSPHINE
Different method of rate determination
PH3 ; PR3 – If auxiliary ligand is phosphine
CONE ANGLE se crowding dekhte hai
Rate of reaction ∝ cone angle of phosphine derivative
Order of Cone angle

Question. [M(PCl3)5X]2+ ; [M(Me3)5X]2+
k1 k2
Answer - k1 > k2
Co3+ d6 low spin ( -2.4∆𝑂 ) → square pyramidal → CFSE = - 2.0 ∆𝑂

→ trigonal bipyramidal → CFSE = - 1.2 ∆𝑂
More stable intermediate chahiye ; compound wants to go in square pyramidal geometry
Dissociation → major intermediate → square pyramidal
But not always
TBP intermediate kaha hoga ?
Hint diya hoga ya koi experimental value di hogi
• Intermediate of 4d and 5d series is always SQUARE PYRAMIDAL because CFSE is
more
• TBP only 3d bna sakta hai
+𝑌
• Trans [M(aa)2X2] −𝑋 Trans [M(aa)2XY] …A
+𝑌
• cis [M(aa)2X2] −𝑋 cis [M(aa)2XY] …B
• A mei intermediate – square pyramidal

• B mei intermediate – square pyramidal
• Agar retention of configuration hogi toh always square pyramidal intermediate

Question. Trans [Pt(en)2Cl2]2+ + 2 Br- P?
Answer – product is Trans [Pt(en)2Br2]2+ ; because 4d and 5d metals hai retention milega
kuki square plyramidal intermediate milega
Question. Cis [Ru(en)2Cl2]2+ + 2 I- P?

Answer – product is Cis [Ru(en)2I2]2+ ; because 4d and 5d metals hai retention milega
kuki square plyramidal intermediate milega
❖ LEARN THIS QUESTION
Cis [Co(en)2Cl Z]2+ cis [Co(en)2__ Z]2+
trans [Co(en)2Cl Z]2+ trans [Co(en)2__ Z]2++ cis [Co(en)2__ Z]2+
This is experimental ; cis se cis mila and trans se mixture

Where Cl is a leaving group ; Z = NO2-, OH- , Cl- , NCS-
trans [Co(en)2Cl Z]2+ Trans (product) Cis (product) Intermediate
Z = OH- 25% 75% TBP
Z = NCS- 35% 65% TBP
Z = Cl- 65% 35% TBP
Z = NO2- 100% 0% SP
Question. {DEC 2016} Hydrolysis of trans [Co(en)2Cl Z]2+ , if the leaving group is Cl .
The formation of cis product is least when Z is
a) OH-
b) NCS-
c) Cl-
d) NO2-
Answer – (d) NO2-

ASSOCIATIVE MECHANISM
[ML5X] +𝑌 [ML5XY] −𝑋 [ML5Y]

Coordination number = 6 mei wahi milta hai jaha low lying d orbitals vacant ho ; like d1, d2
Coordination number = 4 mei mainly milta hai ; in square plannar
We are studying orbital based reaction ; square plannar mei Z – exclusion hai … jaha dz involve hai
wahi padh rhe hai
KINETICS OF ASSOCIATION
𝑘1
[MLnX] + Y [MLnX Y] … fast
𝑘2
[MLnX Y] 𝑘3 [MLnY] + X … slow
Rate = k3 [MLnX Y]
Applying SSA on [MLnX Y]
𝑑
𝑑𝑡
[MLnX Y] = k1 [MLn X] [Y] – k2 [MLnX Y] – k3 [MLnX Y] = 0
k1 [MLn X] [Y] = (k2 + k3) [MLnX Y]
𝑘1[MLnX ][Y]
[MLnX Y] = (k2 + k3)
𝒌𝟑𝒌𝟏[MLnX ][Y]
Rate = (k2 + k3)
𝒌𝒌
𝟑 𝟏
kobs = (k +
2 k3)
Bimolecular – second order – SN2
In coordination number = 4 – intermediate is TBP (trigonal bipyramidal)

FACTORS AFFECTING RATE OD ASSOCIATIVE MECHANISM
Yaha hum chahte hai leaving group kahi na jaaye aur incoming group ko bhi kahe ki
aaja tu bhi
• Rate ∝ 𝑍𝑒𝑓𝑓
• Rate ∝ Oxidation state
1
• Rate ∝
𝑠𝑖𝑧𝑒
1
• Rate ∝
𝑝𝑖 𝑑𝑜𝑛𝑜𝑟
• Rate ∝ 𝑝𝑖 𝑎𝑐𝑐𝑒𝑝𝑡𝑜𝑟

DISSOCIATIVE MECHANISM ASSOCIATIVE MECHANISM
• C. No. = 6 • C. No. = 4
• SN1 • SN2
• Molecularity = 1 • Molecularity = 2
• Intermediate = Square pyramidal • Intermediate = Trigonal
or Trigonal bipyramidal bipyramidal
• Leaving group decides the TAL • TAL decides which one is the
leaving group

COORDINATION CHEMISTRY LECTURE NO. 7(rm)
INTERCHANGE MECHANISM
Two types of activation

• Associative activation Ia
• Dissociative activation Id
ML5X +𝑌 Y---- ML5----X ML5Y

Removal of X is fast ; addition of Y is fast

❑ Associative Ia
Bond formation > bond breaking
❑ Dissociative Id
Bond breaking > bond formation
Interchange mechanism is mostly found in INERT complexes

When coordination number = 6 prefer Id
Question – Which one will give Id and not dissociation reaction

a) If no intermediate is formed
b) If intermediate is highly unstable
c) If leaving group is very poor
d) All of these
Answer – (d)

Question – [ML6]2+ + X- [ML5X] + L
L = neutral monodentate reaction
What is the type of reaction ?
Answer – ANATION reaction = the reaction in which any X- ligand substitutes any neutral ligand
(NH3.H2O)
Question- Which one give Ia and which one will give Id ?
1. [Cr(H2O)6]3+ + X-
2. [Cr(NH3)5(H2O)]3+ + X-
Answer- check formal charge → d3 complexes hai ; inert hai

𝛿+ 𝛿−
Cr - O → charge on metal is more , Zeff is more
Chances of associative mechanism is more
𝛿𝛿 + 𝛿𝛿 −
Cr - N → charge on metal is less , Zeff is less
Chances of dissociative mechanism is more
Answer – 1. – Ia ;2. – Id

Question – [Ru (EDTA) H2O]- + I-
[Ru (EDTA) H2O]2- + I-
They will go through interchange mechanism ; which one will give Ia and Id ?
NOTE : EDTA is a flexidentate ligand and metals of 4d metal make complexes of
coordination number = 6
Therefore, EDTA is a pentadentate ligand here
[Ru(EDTA) H2O]- + I-
x – 4 = - 1 ; x = +3 ;
Ru = d6 s2 ; Ru3+ = d5 inert – this will give associative ; charge is more; Ia
Ru(EDTA) H2O]2- + I-
x – 4 = - 2 ; x = +2 ;
Ru = d6 s2 ; Ru2+ = d6 labile (highly) – this will give dissociative ; charge is less; Id
Question (future year question) –
[Cr (NH3)5 H2O]3+ + X- [Cr (NH3)5 X]3+
X- = NCS- ; Br- ; CF3COO- ; Cl-
Answer – order of rate = NCS- > Br- > CF3COO- > Cl-
Ye learn hi karna padega ; iska koi reason nahi hai

HYDROLYSIS REACTION(in coordination compounds)
Reactions can be hydrolysis (H2O) ; amonolysis (NH3); solvolysis (any solvent)
Complex k sphere mei se ligand hata k agar water molecule lg jaye toh hydrolysis ; amonia lg jaye
toh ammonolysis ; and solvent molecule lg jaye toh solvolysis
Three types of hydrolysis

1. Neutral hydrolysis ; pH = 7
2. acidic hydrolysis ; pH < 7
3. Basic hydrolysis ; pH > 7
NEUTRAL HYDROLYSIS
(dissociative mechanism wala sab same aayega)
SN 1 ; first order ; square pyramidal intermediate
1 1 1
• Rate ∝ 𝑍𝑒𝑓𝑓
; Rate ∝ 𝑂.𝑆.
; Rate ∝ 𝑀𝑋 𝑏𝑜𝑛𝑑 𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ
; Rate ∝ JTD ;
1 1
• Rate ∝ ; Rate ∝ pi- donor ; Rate ∝ ; Rate ∝ Steric crowding
𝐶𝐹𝑆𝐸 𝑝𝑖 𝑎𝑐𝑐𝑒𝑝𝑡𝑜𝑟

Question – if we hydrolyse the following in neutral medium ; pH = 7
I. [ML5F]
II. [ML5Cl]
III. [ML5Br]
IV. [ML5I]
Answer – rate = IV > III > II > I
Question -if we hydrolyse the following in neutral medium ; pH = 7

I. [M(PH3)5X]2+
II. [M(P(OMe)3)5X] 2+
III. [M(PMe3)5X] 2+
Answer – order of cone angle - PMe3 > P(OMe)3 > PH3
rate = III > II > I
Question -if we hydrolyse the following in neutral medium ; pH = 7

I. [Co(NH3)5Cl]2+
II. [Co(NH2R)5Cl] 2+

III. [Co(NHR2)5Cl] 2+
IV. [Co(NR3)5Cl] 2+
Answer – crowding = IV > III > II > I
ACIDIC HYDROLYSIS
𝑘𝑒𝑞
[ML5X]2+ + H+ [ML5X H]3+
conjugate acid
Conjugate acid kab banega ?
Metal k paas jo leaving group hai ; voh basic hona chaiye
CN- and NH3 … which one is basic ?

Answer - CN-
NH3 apne lone pairs pehle ho de gya hai metal ko
CN- k paas N pr lone pair hai
Basic ligand – NO2- ; CN- ; CO32- , HALOGENS
Rate law –
Rate = k2 Keq [complex] [H+]
Rate ∝ [H+]
Question – hydrolysis
[Co (NH3)6 ] 3+ pH = 7 Rate constant = k1
hydrolysis
[Co (NH3)6 ] 3+ pH < 7
Rate constant = k1
a) k1 = k2
b) k1 < k2
c) k1 > k2
d) Not defined
Answer - k1 = k2
Because ligand is not basic ; no conjugate base formed

Question – what is the rate of hydrolysis 1. at pH = 7 ; 2. at pH < 7
1. [Co L5F] 2+ 𝑘1
2. [Co L5Cl] 2+ 𝑘2
3. [Co L5Br] 2+ 𝑘3
4. [Co L5I] 2+ 𝑘4
Answer – pH = 7 ; Co3+→ leaving group I > Br > Cl > F

Therefore, order of rate constant = k4 > k3 > k2 > k1
At pH < 7 ; see basic ligand ; F > Cl > Br > I { H jaldi lega F }

Therefore, order of rate = k1 > k2 > k3 > k4
Question- what is the rate of hydrolysis
[Fe (CN)6 ]4-+ hydrolysis Rate constant = k1
pH = 7
[Fe (CN)6 ]4-+ hydrolysis Rate constant = k2
pH < 7
ANSWER – k2 > k1 ; because CN is a basic ligand

BASIC HYDROLYSIS
[ML5X] + OH-
Auxiliary ligand protic hona chahiye ; OH- usme se H+ nikal lega
[Co (NH3)5Cl] + OH- [Co (NH3)4 NH2Cl] + H2O

conjugate base
𝑘2
[Co (NH3)4 NH2Cl] 𝑘1 [Co (NH3)4 NH2] [Co (NH3)5OH]
−𝐶𝑙 +𝐻2𝑂
NH3 (not donor) NH2- (σ- donor ; ℼ - donor)
−H+

Negative charge Metal k paas jayega aur chlorine ko bahar kr dega; ab Cl araam se nikal
sakte hai
Rate = k1 Keq [complex] [OH- ]

Rate ∝ [OH- ]
Question – compare the rate of hydrolysis of [Co(CN)5 Cl] 3- at

a) pH = 7 ; rate constant = k1
b) pH > 7 ; rate constant = k2
c) pH < 7 ; rate constant = k3
Answer – at pH < 7 ; basic ligand hai … rate jyada hoga
At pH > 7 ; basic medium k liye protic nahi hai iss liye neutral k equal
Therefore, order of rate constants = k3 > k1 = k2
When a reaction is possible in both basic and acidic medium ; we cannot compare them
Question – compare the rate of hydrolysis of [Co(en)2 NH3 Cl] 2+ at
a) pH = 7 ; rate constant = k1
b) pH > 7 ; rate constant = k2
c) pH < 7 ; rate constant = k3
Answer – at pH < 7 ; basic ligand hai … Cl … rate jyada hoga neutral se
k3 > k1
At pH > 7 ; basic medium k liye protic hai ; NH3 ; iss liye neutral se jyada hoga
k2 > k1
We cannot compare k2 and k3
Question – [CSIR NET DEC – 2018] : basic hydrolysis of [Co(trien) NH3 Cl] 2+
1. Red isomer
2. Purple isomer
Answer – Red isomer mei Cl and NH2 aamne saamne hai
Purple isomer mei N and Cl aamne saamne hai
Rate = red > purple
RED ISOMER → TBP intermediate → 100 % retention → NH2 k saamne OH
PURPLE ISOMER → TBP intermediate → Mixture = 85% NH2 k saamne OH and
15% N k saamne OH

Question –
Basic hydrolysis
Cis [Co(en)2Cl2] dil OH- retention of configuration
Basic hydrolysis
Cis [Co(en)2Cl2] inversion of configuration
conc OH-

QUIZ
Question 1 – The reaction [CoCl(NH3)5]2+ + OH- giving [Co(OH) (NH3)5]2+ follows a mechanistic
pathway which is
a) SN1
b) SN2
c) SN1CB
d) SE2
Answer – basic medium hai ; protic ligand present hai
Rate = k1 Keq [complex] [OH- ]
Answer – (c) SN1CB
Question 2 – Which one of the following complex is kinetically inert in a solution
a) [Cr(H2O)6]2+
b) [Cr(H2O)6]3+
c) [Co(H2O)6]2+
d) [Ni(CN)4]2-
Answer – (b) [Cr(H2O)6]3+ Dr. Kuldeep Garg (KDSIR CLASS NOTES) 382
Question 3 – The substitution reaction of [Co (CN)5 Cl]3- with OH – to give [Co
3- 2+
(CN)5 OH] in comparison to that [CoCl(NH3)5] to give [Co(OH) (NH3)5] is 2+
a) Slow and rate depends only on [Co (CN)5 Cl]3-

b) Fast and rate depends only on [Co (CN)5 Cl]3-
c) Slow and rate depends on [Co (CN)5 Cl]3- and OH –
d) Fast and rate depends on [Co (CN)5 Cl]3- and OH –
Answer – (a)
Question 4 – The rate of exchange of H2O present in the coordination sphere by 18 H2O
of
(i) [Cu(H2O)6]2+ (ii) [Mn(H2O)6]2+ (iii) [Fe(H2O)6]2+ (iv) [Ni(H2O)6]2+
Follows the order
a) (i) > (ii) > (iii) > (iv)
b) (i) > (iv) > (iii) > (ii)
c) (ii) > (iii) > (iv) > (i)
d) (iii) > (i) > (iv) > (ii)
Cu2+ → d9 ; Mn2+ → d5 ; Fe2+ → d6 ; Ni2+ → d8
Answer – (a) (i) > (ii) > (iii) > (iv)
Question – 5 – What is the product X in the following reaction ?
Answer – (C)

Question- 7 – In the following reaction
[PtCl4]2- + NO2- A + NH3 B
Compound B is
a) Trans – [PtCl2 (NO2) (NH3)]-
b) Cis – [PtCl2 (NO2) (NH3)]-
c) Trans – [PtCl2 (NH3) 2]
d) Cis – [PtCl2 (NO2)2]-
Answer –
Question – 8 – the water exchange rates for the complex ions follows the order
a) [V (H2O)6 ]2+ > [Co (H2O)6 ]2+ > [Cr (H2O)6 ]3+
b) [Cr (H2O)6 ]3+ > [Co (H2O)6 ]2+ > [V (H2O)6 ]2+
c) [Co (H2O)6 ]2+ > [Cr (H2O)6 ]3+> [V (H2O)6 ]2+
d) [Co (H2O)6 ]2+ > [V (H2O)6 ]2+ > [Cr (H2O)6 ]3+
Answer – V2+ → d3 ; Co2+ → d7 ; V3+ → d3
inert labile inert
Answer (d) [Co (H2O)6 ]2+ > [V (H2O)6 ]2+ > [Cr (H2O)6 ]3+
Question 9 -
The isomers A and B undergo hydrolysis by forming a trigonal bipyramidal intermediate . The
correct statement is
a. A reacts faster than B and both result in a mixture of products
b. B reacts faster than A and both result in a mixture of products

c. A reacts faster than B and B results in a mixture of products
d. B reacts faster than A and A results in a mixture of products
ANSWER - c. A reacts faster than B and B results in a mixture of products
Question- 10 – the correct statement regarding the thermodynamic stability and kinetic reactivity
of metal ion complexes is that
(a) More stable complexes are less reactive
(b) There exists a dependence on the bulkiness of the ligand
(c) There exist no direct relation between these two phenomenons
(d) There exist a dependence on the size of the metal ion
Answer – (c)
Question 11 – which one of the following configuration kinetically inert octahedral complexes
a. t2g6 eg0
b. t2g3 eg1
c. t2g5 eg0
d. t2g6 eg4
Answer – (a)
Question 12 – the acid catalysed hydrolysis of trans – [Co(en)2 A X ] n+ can give cis
product due to formation of
a. Square pyramidal intermediate
b. Trigonal bipyramidal intermediate
c. Pentagonal bipyramidal intermediate
d. Face capped octahedral intermediate
Answer – trans se cis mil rha hai … trigonal bipyramidal intermediate (b)

SUBSTITUTION REACTION IN C. NO. =4 IN SQUARE PLANNAR
Hybridisation of square planar complexes → dsp2 , sp2d
Z is not involved in the hybridisation

sp2d → s, px , py , dx2-y2
These are Z-excluded compounds ; therefore easier to study
3d series k metals mei

1) d7 → Co2+ → dsp2 (paramagnetic)
2) d8 → Ni2+ → dsp2 (diamagnetic) with strong ligand
3) d7 → Cu2+ (with py , NH3 , en , CN ) → paramagnetic
4d → Ru Rh Pd Ag make square planar

5d → Os Ir Pt Au (all are diamagnetic)
O.S. = 0 +1 +2 +3 (all are dsp 2)
these all are converted d8 systems
[Rh (PPh3)3 Cl ] → Wilkinson catalyst
[Rh (CO)2 I2 ]+ → Diamagnetic → dsp2
Ru → d6s2 → d8 converted compound
NOTE :
[Pd (PPh3)3 Cl ]+ → square planar
[Pd (PPh3)4 ]2+ → not stable in square planar geometry
Question - Ru (0) ; Os (0)

[Ru (dppE)2 ] ; [Os (dmpE)2 ] inka structure kya hoga ?

[Ru ((CH2 P(Ph)2)2)2] – neutral ligand hai
Ru0 → d8 converted – square planar
[Os ((CH2 P(Me)2)2] – neutral ligand hai

Os0 → d8 converted – square planar
Wilkinson catalyst - [Rh (PPh3)3 Cl ] →dsp2
Ziess’s salt – [Pt Cl3 (C2H4) ] - → Pt2+– square planar

Example –
[Au F4]- → Au3+– square planar
[Ag F4]- → Ag3+– square planar
What is the structure of [Pd (PNP) CH3 ] ?

PNP = N,N’-bis(diphenylphosphine)-2,6-di
PNP is a negative ligand

C.No. = 4 ; Ni2+ ; Pt2+ ;Pd2+ ; Au2+ → d8 complexes
Rate of substitution = Ni2+ > Pt2+ > Pd2+ < Au2+

KINETICS
Rate = k1[complex] + k2[complex][Y]
first order second order
[Y] pr rate depend karta hai …
if concentration of Y is excess → Rate is pseudo first order reaction
If [Y] is not in excess → reaction is second order reaction
Rate = [complex] [k1 + k2[Y]]
Rate = Kobs [complex]
Where, Kobs= [k1 + k2[Y]]
If [Y] = excess ; Kobs= k1

• Intermediate formed here is TBP
• Mechanism is associative
• We get retention of configuration
• SOLVATO MECHANISM – if solvent behave as nucleophile; pehle solvent jaake
lag jayega … uske baad main ligand solvent ki jagah lag jayega

When solvent takes part in the reaction
Rate = k1[complex][S] + k2[complex][Nu] → second order kinetics
Rate ={ k1 [S] + k2 [Nu]} [complex]

Rate = Kobs [complex]
Where; Kobs ={ k1 [S] + k2 [Nu]}
TRANS EFFECT
Trans effect depends upon two things
TI = trans influence – ground state effect – thermodynamic effect
TS = transition state – excited position effect – kinetic effect
CN > CO > NO > C2H5 > PR3 > H > C6H5 > NO2 > I > SCN > Br > Cl > Py > NH3 >
OH- > H2O
COORDINATION CHEMISTRY LECTURE NO. 9(RM)
Trans effect
1. TIE – ground state pr lagta hai
2. TSE – excited state pr lagta hai
Ye dono effect TAL ki wajah se lagte hai
Rate is highly affected by TAL in square planar complexes

CAL se bhi effect lagega – crowding effect ; lekin ye minor hoga
If crowding is more – rate of reaction should be slow
Here we are not studying dissociative mechanism, we are studying associative

mechanism
1
Crowding ∝ 𝑟𝑎𝑡𝑒 this is for associative mechanism

TIE – thermodynamic effect → sigma bond tendency or sigma donor capacity or sigma
bond strength .
Sigma bond jo jyada ache se kama raha hoga uska trans influence utna jyada hoga
H > CH3
H is better sigma donor
Ground state se excited state mei

jaane ko ready hai
Transition state → excited position effect → KINETIC EFFECT → pi acceptor tendency
Metal k electron leke beth jayega TAL fir metal associate karega incoming ligands ko ;
If transition state is stable ; reaction will go in forward reaction

Trans influence ground state effect → ground state ki energy increase kr rha hai
Transition state – excited state effect → excited state ya transition state ki energy
decrease kr rha hai
Pi acceptor is given more priority over sigma donor when we have to do comparison
TRANS INFLUENCE EFFECT (BASED ON SIGMA DONOR)

H- > CH3- > Ph- > I- > Br- > Cl- > F- > OH- > H2O
Which ligand will leave ?
Answer. Trans to H- ; therefore OH- will leave
TRANS EFFECT SERIES

CN > CO > NO > C2H5 > PR3 > H > C6H5 > NO2 > I > SCN > Br > Cl > Py > NH3 >
OH- > H2O
To learn : sana koi no ithe priya hai methai fana nahi aai thi bread khaale pyaaari amma
hydroxy water
TAL = CO
TAL = NO2

EXCEPTION :
Cl ka trans effect jyada hai

Pt-N bond is very strong → majboori mei tootega
NH3 k saamne wala Cl nahi nikaaal sakte kuki NH3 ka trans effect itna nahi hai ki
Cl ko nikaal de
PLATIN –
1. CIS PLATIN – Cis [Pt (NH3) Cl2 ]
2. TRANS PLATIN – trans [Pt (NH3) Cl2 ]
KURNAKOV TEST
Cis and trans platin are identified by this test

Reagent used in this test is THIOUREA , NH2-CS-NH2
Trans effect - NH2-CS-NH2 > Cl- > NH3
Cis platin and trans platin + thiourea (TU)

SUBSTITUTION IN TETRAHEDRAL COMPLEXES
Interchange assosiation (SN2) or Interchange dissociation (SN1)
Ni(CO)4 PPh3
Reaction association se hogi ya dissociation se ?
Answer – dissociation
Because Ni(CO)4 follows 18 electron rule → we get dissociation reaction
Where 14 and 16 electron rules are followed → we get association
PPh3
[Co (CO)3 NO ] DISSOCIATION ASSOCIATION
x + 3 (0) + 1 = 0 ; x = -1
Co-1
Number of electron = [Co (CO)3 NO ] if Co-1 and NO+
[ 10 +6 +2 ] → 18 electrons
THIS IS WRONG
Number of electron = [Co (CO)3 NO ] if Co+ and NO- (Internal e- transfer)
[ 8 +6 +2 ] → 16 electrons – Association
[Co (CO)2 NO PPh3] ; Co is in -1 and NO is in +1
ELECTRON TRANSFER REACTION

Electron transfer reaction is of two types
1. Complementary
2. Non complementary
COMPLEMENTARY
Sn2+ + Ti3+ Sn4+ + Ti1+

Difference in oxidation state of oxidant and reductant is same
Sn2+ → Sn4+
Ti3+ → Ti1+
Dono mei change 2 ka hai

NON COMPLEMENTARY
We donot have to study this ; it is very difficult ; matter of research
Difference same nhi hai
Cr (IV) + 3 Fe (II) Cr (III) + 3 Fe (III)
Cr (IV) Cr (III) { +1 ka change }

3 Fe (II) 3 Fe (III) { +3 ka change }

Complementary electron transfer reactions
❑ One electron transfer (in complex)
• Inner sphere mechanism {bridging ligand is must}
➢Adjacent attack
L5M---Cl---ML5 (bridging ligand ki similar side se juada hai
Electron metal se )
transfer via ➢Remote attack
bridging L5M---SCN---ML5 (bridging ligand different side se juada
ligand hai metal se )
• Outer sphere mechanism{bridging ligand is not must}
➢Simple reaction
Electron [Fe (H2O)6]3+ + [Fe* (H2O)6]2+
transfer via ➢Cross reaction
quantum [Fe (H2O)6]3+ + [Ru (NH3)6]2+
tunelling
❑ Two electron transfer

INNER SPHERE MECHANISM

• Bridging ligand is must ; Electron transfer via bridging ligand
• In outer sphere mechanism ; no bridging ligand ; electron transfer cannot take place
via bridging ligand ; electron transfer via tunneling
• STEPS OF INNER SPHERE MECHANISM

1. Association
2. Bridge formation
3. Electron transfer
4. Bridge breaking
5. Aquation
• [Co (NH3)5 Cl ]2+ (aq) + [Cr (H2O)6 ]2+ (aq)

• Inert (generally) labile
• [Co (NH3)5 Cl ]2+ (have bridging ligand ; labile ya inert kuch bhi ho sakta hai ; lekin
water se react nhi karega agar labile hoga )
[Co (NH3)5 Cl ]2+ (aq) + [Cr (H2O)6 ]2+ (aq)
association
[Co (NH3)5 Cl ]2+ -------- [Cr (H2O)6 ]2+ (aq)

bridge formation
[(NH3)5 Co ]2+ ------ Cl ------- [Cr (H2O)6 ]2+
[(NH3)5 Co3+ ------ Cl ------Cr 2+ (H2O)6 ]4+

electron transfer Cr2+ se Co3+ electron transfer
[(NH3)5 Co2+ ------ Cl ------Cr 3+ (H2O)6 ]4+

bridge breaking Cl will go to inert
Cr3 + → d3 - inert
[Co (NH3)5 ]2+ (aq) + [Cr (H2O)5 Cl ]2+ (aq) Co2 + → d7

[Co (NH3)5 ]2+ (aq) H2O [Co (H2O)6 ]2+ (aq)
labile aquation
RATE DETERMINING STEP
Jo step hona nahi chahta ; slow hoga ; rate determining step hoga
1. Association – no problem
2. Bridge formation – no problem
3. Electron transfer – labile se inert ; ek inert se labile {aisa ku hone dega}
Generally, electron transfer is a slow step and rate determining step
❖ When bridging ligand is good
❖ Complex without bridging ligand is labile
If compound without bridging ligand is inert

Then RDS changes; say , [Cr (H2O)6 ]2+ - labile is replaced by [V (H2O)6 ]2+ - inert
Bridge formation gets difficult because both are inert

Therefore, RDS is bridge formation
IF ELECTRON TRANSFER IS THE RDS

• Good bridging ligand
• Non bridging complex – labile
after electron transfer
Inert ------bridge------labile
Labile------bridge-------inert
If inert-------bridging ligand-------- inert

Now RDS is bridge breaking because bridging ligand will get confused ki mae kaha jau ?
90% case – bridging ligand does not transfer
Ex - [Ru (NH3)5 Cl ]2+ + [Cr (H2O)6 ]2+ (in this case bridge breaking is the RDS)
after electron transfer

[Ru (NH3)5 ]2+ (Inert) + [Cr (H2O)6 ]3+ (Inert)
[Ir Cl6 ]2- (aq) + [Cr (H2O)6 ]2+ (aq)
association
[Cl5 Ir4+ ------ Cl ------Cr 2+ (H2O)6 ]0

electron transfer
[Cl5 Ir3+ ------ Cl ------Cr 3+ (H2O)5 ]0

Inert d6 Inert d3
bridge breaking
Dr. KULDEEP GARG
[Ir Cl6 ]3- (aq) + [Cr (H2O)6 ]3+ (aq)
[Fe (CN)6 ]3- (aq) + [Co (CN)6 ]3- (aq)
association
[(CN)5 Fe3+ ------ CN ------Co 3+ (CN)5 ]6-

electron transfer
[(CN)5 Fe2+ ------ CN ------Co 4+ (CN)5 ]6-
bridge breaking
[Fe (CN)6 ]4- (aq) + [Co (CN)5 H2O]2- (aq)

d6 low spin (inert) d6 low spin (inert)
Partially remote attack – Fe-C bond is stronger than Co-N bond

RDS is bridge breaking {LEARN}
REMOTE ATTACK
M -----SCN------M
Example - [Co (NH3)5 (SCN) ]2+ (aq) + [Cr (H2O)6 ]2+ (aq)
Remote attack
[Co (H2O)6 ]2+ + [Cr (H2O)5 (NCS) ]2+ + [Cr (H2O)5 (SCN) ]2+
70% 30%
SCN = S se juda tha in reactant
SCN = N se juda in product
[(NH3)5 Co3+ ------ SCN ------Cr 2+ (H2O)5 ]

electron transfer
[(NH3)5 Co2+ ------ SCN ------Cr 3+ (H2O)5 ]

Labile inert
bridge breaking

[Co (NH3)5 ]2+ (aq) + [Cr (H2O)5 (NCS) ]2+ ( 70%)
H2O
[Co (NH3)5 ]2+ (aq) [Co (H2O)6 ]2+ (aq)
labile aquation
Sulphur can make bridge like
[(NH3)5 Co2+ ------ S ------Cr 3+ (H2O)5 ]

CN
This is known as adjacent attack
Therefore, [Cr (H2O)5 (SCN) ]2+ (30%)

[Co (NH3) X ] + [Cr (H2O)6 ]
Rate depends on X ligands

1. Inorgaanic – more polarisibilty ; rate fast
2. Organic - -I effect more ; rate fast
No comparison between inorganic and organic ligand
Example : H2O ; NCS ; SCN ; F ; Cl ; I

Order of polarisibility – I > Cl > F > SCN > NCS > H2O > NH3
(fastest) (slowest)
Question – X kb dekhna hai ?
When RDS is electron transfer. Rate of reaction depends upon transfer of electron via
bridging ligand
Jb bridging ligand easily electron transfer karva de – rate jyada
ORGANIC LIGANDS
Rate = IV > III > II > I
SUMMARY OF INNER SPHERE MECHANISM

• Good bridging ligand
• Complex without bridging ligand is labile
➢ RDS = electron transfer

• When complex without bridging ligand is inert say [V (H2O)6]2+
RDS = bridge formation
• After electron transfer; if we get inert-----bridging ligand-----inert
RDS = bridge breaking
• When remote attack is mentioned in case of SCN ligand – NCS wala product
• When adjacent attack is mentioned in case of SCN ligand – SCN wala product
• When nothing is mentioned – NCS ( 70%) + SCN (30%)
OUTER SPHERE MECHANISM
Simple – Fe-Fe (graph based question)

Cross – Fe-Ru (numerical based question)
[M(n+1) Lx ] + Mm+ Ly
M is same ; M can be different
Conditions
• Non bridging complex should be inert 5%
• No bridging ligand 95%
❖ Rate of outer sphere reaction is 104 times slower than inner sphere reaction
❖ In outer sphere – electron transfer through tunneling
❖ Tunneling tb hoti hai jb dono complex ki bond length ek jaisi ho jaye due to
vibration – elongation and compression
❖ Rate of vibration is 104 times slower than electron transfer
❖ Vibration hone k baad electron transfer hoga iss liye outer sphere reaction 104
times slower hogi

Mechanism –
1. [Mn+1Lx] + [Mm+Ly] [Mn+1Lx -------Mm+Ly]
Precursor complex
2. Reorganisation of precursor complex (through solvent)

3. Electron transfer
[Mn+1Lx -------Mm+Ly] [Mn+1Lx] + [Mm+Ly]
4. Dissociation of successor complex

[Mn+Lx -------Mm+1Ly] [Mn+Lx] + [Mm+1Ly]

‡ ‡ ‡ ‡
∆𝐺 = ∆𝐺 t + ∆𝐺 o + ∆𝐺 i
‡
∆𝐺 t = energy used to bring the complexes near and far in first step and last step
‡
∆𝐺 o = energy used for organisation by solvent
‡
∆𝐺 i = energy required to make bond lengths equal

Fe2+→ bond compression
Gap is less , when ligand will come closer ; repulsion will increase ; splitting will
increase
Fe3+→ bond elongation

When ligand will go far, repulsion decrease; splitting will decrease
RATE OF OUTER SPHERE REACTION
Depends upon 2 factors. (experimentally observed)
1
Rate ∝
∆𝑑
∆𝑑 = change required in bond length
Rate ∝ 𝜋 − 𝑎𝑐𝑐𝑒𝑝𝑡𝑜𝑟 𝑙𝑖𝑔𝑎𝑛𝑑
Question –
I. [Cr* (H2O)6 ]2+ + [Cr (H2O)6 ]3+ → [Cr* (H2O)6 ]3+ + [Cr (H2O)6 ]2+
II. [V* (H2O)6 ]2+ + [V (H2O)6 ]3+ → [V* (H2O)6 ]3+ + [V (H2O)6 ]2+
Which reaction will be faster ?
Answer – Cr2+ → d4 ; Cr2+ → d3 → bond length mei difference jyada
Strong JTD
V2+ → d3 ; V3+ → d2 → bond length mei difference kum – Rate faster
Slight JTD
Answer – II > I
Question –
I. [Co* (NH3)6 ]3+ + [Co (NH3)6 ]2+ → [Co* (NH3)6 ]2+ + [Co (NH3)6 ]3+
II. [Ru* (NH3)6 ]3+ + [Ru (NH3)6 ]2+ → [Ru* (NH3)6 ]2+ + [Ru (NH3)6 ]3+
Which reaction will be faster ?
Answer – Co3+ → d6 (L.S) ; Co2+ → d7 (H.S) → bond length mei difference jyada
Strong JTD kuki ∆𝑜 mei difference jyada – Rate km
Ru3+ → d5 (L.S) ; Ru2+ → d6 (L.S)
Answer – II > I
Question.
I. [Ru* (NH3)6 ]3+ + [Ru (NH3)6 ]2+ → [Ru* (NH3)6 ]2+ + [Ru (NH3)6 ]3+
II. [Ru* (bpy)3 ]3+ + [Ru (bpy)3 ]2+ → [Ru* (bpy)3 ]2+ + [Ru (bpy)3 ]3+
Ru3+ → d5 (L.S) ; Ru2+ → d6 (L.S)
III. [Fe* (bpy)3 ]3+ + [Fe (bpy)3 ]2+ → [Fe* (bpy)3 ]2+ + [Fe (bpy)3 ]3+
bpy = pi – acceptor ligand

Rate ∝ pi – acceptor ligand
II , III > I
Ru and bpy – distance between bond is less . Therefore rate is more
Answer – II > III > I
RATE DETERMINING STEP
RDS is always electron transfer
𝐾𝑏 𝑇 ∆𝐺
Rate of reaction, Kr = exp(− )
ℎ 𝑅𝑇
Self exchange reaction, ∆𝐺° = 0

Kuki reactant and product is same
MARCUS EQUATION
𝟏 ‡
∆𝑮 = 𝝀 + 𝜟𝑮° 𝟐
𝟒𝝀
𝜆 = 𝑅𝑒𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 𝑣𝑖𝑎 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑜𝑟 𝑏𝑜𝑛𝑑 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑜𝑟 𝑒𝑙𝑜𝑛𝑔𝑎𝑡𝑖𝑜𝑛
𝜆 = minima of reactant curve se ek line jaha P ko touch kre

COORDINATION CHEMISTRY LECTURE NO. 12
‡
When Δ𝐺 = 0 ;
Kr = maximum rate
𝐾𝑏 𝑇 ‡
Kr = ℎ
at Δ𝐺 = 0
‡
Δ𝐺 = 0 , rate of reaction is maximum
Find the relationship between Δ𝐺° 𝑎𝑛𝑑 𝜆
Δ𝐺° = 𝜆 Δ𝐺° > 𝜆 Δ𝐺° < 𝜆

‡ 1 2
∆𝐺 = 𝜆 + Δ𝐺°
4𝜆
When Δ𝐺° = 𝜆 (𝜆 is negative)
‡ 1 2 ‡
∆𝐺 = 𝜆−𝜆 ; ∆𝐺 = 0 {rate is maximum}
4𝜆
When Δ𝐺° > 𝜆
‡ 1 2 1 ‡
∆𝐺 = 𝜆 + Δ𝐺° = 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑡𝑒𝑟𝑚 ; ∆𝐺 > 0
4𝜆 4𝜆
When Δ𝐺° < 𝜆
‡ 1 2 1 ‡
∆𝐺 = 𝜆 + Δ𝐺° = 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑡𝑒𝑟𝑚 ; ∆𝐺 > 0
4𝜆 4𝜆

I = normal region – Δ𝐺° < 𝜆 [As Δ𝐺° increases ; rate increases ]
II = inverted region - Δ𝐺° > 𝜆 [As Δ𝐺° increases ; rate decreases ]
Question [GATE 2005]

The potential energy versus reaction coordinate diagram
For electron transfer reaction, rate constant k1 , k2 , k3 are given below
The increasing order of rate constant

Answer – (d) k3 < k1 < k2
For k2 -Δ𝐺° = 𝜆 (𝜆 is negative)
‡ 1 2 ‡
∆𝐺 = 𝜆−𝜆 ; ∆𝐺 = 0 {rate is maximum}
4𝜆
RATE IN CROSS REACTION
Rate , k12 = [ k11 k22 K12 f ]1/2

k = rate constant
K = equilibrium constant
k12 = rate constant of cross reaction
K12 = equilibrium constant for overall reaction
f = sterric factor ; if not given ; f = 1
k11 and k22 = rate constant for two self exchange reaction
k11
[Fe (H2O)6 ] 3+ [Fe (H2O)6 ] 2+
k22
[Ru (NH3)6 ] 2+ [Ru (NH3)6 ] 3+
Keq
[Fe (H2O)6 ] 3+ + [Ru (NH3)6 ] 2+ [Fe (H2O)6 ] 2+ + [Ru (NH3)6 ] 3+
1 2 1 2
Question –
k11 = 4.2 L mol-1 s-1
k22 = 4.0 × 10 3 L mol-1 s-1
Keq = 2.11 × 10 11
f = 0.85
Calculate k12
Answer – k12 = [ k11 k22 K12 f ]1/2
k12 = [4.2 × 4.0 × 10 3 ×2.11 × 10 11 ×0.85]1/2
k12 = [30.1308× 1014 ]1/2
k12 = 5.48× 107 L mol-1 s-1

Marcus theory
Rate of self exchange and cross reaction ko compare krvane ka question aa sakta hai
NOTE – cross section ka rate is greater than self exchange reaction ka rate
(when compounds are same )
CSIR NET 2016 (4 MARKS)

In the following redox reaction with an equilibrium constant Keq = 2.0 × 10 8
The self exchange rate for oxidant and reductant are 5.0 s-1 M-1 and 4.0 × 10 3 s-1 M-1 . The
approximate rate constant for the reaction in M-1 s-1
(a) 3.16 × 10 6
(b) 2.0 × 10 6
(c) 6.32 × 10 6
(d) 3.16 × 10 4
Answer – k12 = [ k11 k22 K12 f ]1/2
k12 = [5.0 × 4.0 × 10 3 ×2.0 × 108 × 1]1/2

k12 = [4.0 × 1012 ]1/2
k12 = 2.0 × 106
Answer – (b)
THANKS
Dr. KULDEEP GARG

COORDINATION (With Reac. Mech) PPT Notes BY DR. Kuldeep Garg

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COORDINATION CHEMISTRY

CLASS NOTES FOR CSIR-NET/GATE/IIT JAM/TIFR/BARC/GSI

By–Dr. KULDEEP GARG (KD SIR)

For more notes follow my telegram channel- kuldeepgargchemistry

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 1

Complete Coordination Chemistry

Question 2 – What is the hybridisation of [Re(CH3)6] and [W(CH3)6] ?

Dono ki geometry = Triagonal prismatic

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 4

Stability is a relative phenomenon. Stability alag alag type ki hoti hai.

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 5

❖ d block mei thermodynamic stability formal charge k basis pr nhi dekhni h

Question – what is the formal charge on [Ni(CO)4] and [Ni(Cl)6]2- ?

Mo ki -4 O.S. tk jaata hai

• For 3d metals – 5 > 6 > 4 > 3 membered ring

• acac - acetoacetate – iske saath metal 6 membered ring banata hai

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 10

Ab sab doubts finish … ab padhna start karenge

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 11

Pauling gave a theory … theories hai … concept nhi hai …

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 13

Hydrogen k paas kitne orbitals hote h ?

H k orbitals mei de dete electron … usko ku nhi diye

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 14

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 15

Hexagonal planar Trigonal prismatic Octahedral

Molecular formula – Cr(NH3)6Cl3

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 17

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 18

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 19

POSTULATES OF WERNER THEORY

Primary valency → Oxidation state of central metal atom

Primary valency is ionizable, whereas secondary valency is non-ionizable

Primary Valency can be satisfied only by negative ion

Primary valency → O.S. → Ionizable → negative → non-directional

Secondary valency → C.N. → non-ionisable → negative / neutral → directional

Bonding nature of M-L bond Dr. KULDEEP GARG

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 23

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 24

We know, Oxidation state increase ; stability increase

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 25

Ligand k basis pr stability nahi bata sakte

Charge pr based stability only p – block mei bata sakte hai

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 26

Summary for non transition metals

THIS STABILITY IS THERMODYNAMIC STABILITY

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 27

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 28

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 29

❑ [Cu(NH3)4] and [CuF6]4-

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 30

Coordination number depends upon –

[Cu (H2O)6] and [Ni (H2O)6] exist because Oxygen is electronegative.

Dr. Kuldeep Garg (KDSIR CLASS NOTES) 32

Ab tk humne dekha ki electroneutrality k according

• Ligand mei bhi hum 2 cheeze dekhenge

Ligands are classified on the basis of donation

Classical – jo apna kaam ek dm perfectly kare