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CHAPTER 2. COORDINATION COMPOUNDS (9 marks)

Differences between Double salts & Complex salts
Double salts Complex salts
* Double salt gives a mixture of two salts (2 cations ) * Complex salt do not give a mixture of two Salts
when added to water. when added to water. They give complex ion.
* Their solutions answer for all the ions indicated in * Their solutions does not answer for all the ions
the formula. indicated in the formula.
Examples: Examples:
1. Potash Alum : 1. Potassium ferrocyanide :
+ 3+ 2–
K2SO4.Al2(SO4)3.24H2O →2K + 2Al +4SO4 K4[Fe(CN)6] → 4K+ + [Fe(CN)6]4–

2.Carnallite : 2.Cuprammonium sulphate :

KCl.MgCl2.6H2O → K++ Mg2++3Cl– [Cu(NH3)4]SO4 → [Cu(NH3)4]2+ + SO42–

3.Mohr's Salt : 3.Cobalt hexaammine chloride :

FeSO4.(NH4)2SO4.6H2O →Fe2++2NH4++2SO42– [Co(NH3)6]Cl3→ [Co(NH3)6] 3+ + 3Cl–

Meaning of a coordination compound or complex compound

Transition Coordinate Electron

Metal ion bond pair donors

Terminology in coordination chemistry :

1. Coordination compound: It is a compound formed by the combination of a transition metal ion or atom
and a fixed number of other ions or molecules(ligands) joined through co-ordination bonds. They dissociate in
water to give at least one complex ion. They are also called Complex salts.
Examples : Cobalt hexaammine chloride [Co(NH3)6]Cl3
Potassium ferro cyanide K4[Fe(CN)6]
Cuprammonium sulphate [Cu(NH3)4]SO4

2. Coordination entity: A coordination entity is the combination of central metal ion or atom bonded to a
fixed number of ions or molecules(ligands).
Example (i) In [Co(NH3)6]Cl3 , Cobalt ion is bonded to 6 ammonia NH3 molecules .
Example(ii) In K4[Fe(CN)6], Iron ion atom is surrounded by 6 cyanide CN- ions.
Note : [PtCl2(NH3)2], [Ni(CO)4] , [CoF6]3- are other examples.

3. Central metal ion / atom : It is the metal ion / atom to which a fixed number of ions/groups are joined in a
definite geometrical arrangement in the coordination entity. These central atoms/ions are considered as Lewis
acids (electron pair acceptors) . Examples :
(a) In [Co(NH3)6]Cl3 , the central metal ion is Co3+ (b) In [NiCl2(H2O)4] , the central metal ion is Ni2+
(c) In [CoCl(NH3)5]2+ , the central metal ion is Co3+ (d) In [Fe(CN)6]3– , the central metal ion is Fe3+

4. Oxidation number of central atom : The oxidation number of the central atom is the charge it would carry
when all the ligands are removed along with shared electron pairs. It is also called primary valency.
Eg : In [Co(NH3)6]Cl3, central metal ion is Co3+. Oxidation number is +3.
In [NiCl2(H2O)4] , central metal ion is Ni2+ & oxidation number is +2.
In [Fe(CN)6]3– , central metal ion is Fe3+ . Hence oxidation number is +3.
Note: The oxidation number is represented by a Roman numeral in parenthesis following the name of the
coordination entity. Eg: Oxidation number of copper in [Cu(CN) 4] 3– is +1. Hence it is written as Cu ( I ) .
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5. Ligands : These are the ions or molecules bonded to central atom/ion in the coordination entity.
(They donate at least one electron pair to central metal ion )
Examples: : In [Co(NH3)6]Cl3 , the ligands are 6 NH3 molecules.
Note1. They may be simple ions like CN– , Cl– , F– ..or small molecules such as H2O, NH3 , CO ....or big
molecules such as H2N-CH2-CH2-NH2 , N(CH2CH2NH2)3
Note : Even macromolecules like proteins can act as Ligands.

6. Coordination number: The coordination number (C.N) of a metal ion in a complex is defined as the number
of ligand donor atoms to which the metal is directly bonded. It is also called secondary Valency.
Example : In the complex In [Co(NH3)6]Cl3 , the coordination number of Co is 6 .
Note: Coordination number is determined only by the number of sigma bonds formed by the ligand with the
central atom / ion. If Pi bonds are formed between the ligand and the central atom/ion , they are not counted for
this purpose.

Question: Find coordination number in the following complexes:

(i) [Ni(NH3)4]2+ : In this complex, Four NH3 molecules are ligands.
Each NH3 has one donor atom (unidentate ligand). Hence the coordination number of Ni is 4 .
(ii) [Fe(C2O4)3]3– : In this complex , Three oxalate ions are ligands. Each C2O42– has two
donor atoms (Didentate ligand). Hence coordination number of Fe is 6.
(iii) [Co(en)3]3+ : In this complex, Three en or ethane-1,2-diamine molecules are Ligands. Each en has two
donor atoms (Didentate Ligand) . Hence coordination number Co is 6.

7. Coordination sphere : The central atom / ion and the ligands attached to it are enclosed in
square bracket and is collectively termed as the coordination sphere. The ionisable groups are written outside
the bracket and they are called counter ions.
Example : Consider the complex [Co(NH3)6]Cl3 .
The coordination sphere is [Co(NH 3)6]3+ and the counter ion is Cl-

8. Homoleptic and Heteroleptic complexes :

( What are Homoleptic and Heteroleptic complexes ? Give one example for each.)

(i) Homoleptic complexes are the complexes in which the central metal ion is bonded to only one kind of donor
groups or ligands .
Example: [Co(NH3)6] 3+ . Six NH3 molecules are ligands.
(ii) Heteroleptic complexes are the complexes in which the central metal ion is bonded to more than one kind of
donor groups or ligands.
Example: [Co(NH3)4Cl2] + . Four NH3 molecules and Two Cl- ions are ligands.

Types of Ligands : These are the ions or molecules bonded to the central atom / ion in the coordination entity .
They may be simple ions or molecules having one or more donor atoms.
The number of such ligating atoms is called the Denticity of the ligand.

1. Unidentate ligands : These are the ligands which form Examples : F– , Cl–, Br – , I– , CN–, OH–
one co-ordinate bond through one ligating atom (donor NH3 , H2O , CO, NO,
atom) .

2. Didentate ligands : These are the ligands which form Examples : C2O42– or or ox [oxalate ion]
two co-ordinate bonds through two donor atoms.
H2N-CH2-CH2-NH2 or en [ethane-1,2-diamine]
(ethylene diamine)
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3. Poly dentate ligand : These are the ligands which form Example: CH2-COO–
more than three co-ordinate bonds through more than three CH2-N CH2-COO–
donor atoms. CH2-COO–
CH2-N CH2-COO–
ethylene diamine tetraacetate ion or edta4- .
It is a hexa dentate ligand.

4. Ambidentate ligand: This ligand has two donor atoms Example 1. NO2– nitrito ligand
but use only one donor atom to form coordinate bond with
central metal ion.

Example 2. SCN– thiocyanato ligand

5. Chelating ligand: It is a ligand with two or more donor Example: H2N-CH2-CH2-NH2 or en

atoms so that it forms a ring structure through coordinate [ethane-1,2-diamine] or (ethylene diamine)
bonds.

WERNER THEORY OF COORDINATION COMPOUNDS.

Werner in 1898, proposed the theory of coordination compounds. The main postulates are:

1. In coordination compounds, Transition metals show two types of valences:

(a) primary valency : It is variable and (b) secondary valency. It is fixed.
2. The primary valency is ionisable and it is generally satisfied by negative ions.
[ This results in the formation of simple salts like CoCl 3, FeSO4 , CuSO4 ]
3. The secondary valency is non ionisable and is equal to the coordination number of metal.
They are satisfied by neutral molecules or negative ions (ligands).
[This results in the formation of Complex salts ]
4. The secondary valences have characteristic spatial arrangements for different coordination numbers.
Hence coordination compounds have definite geometrical shapes(Polyhedrons).
Note: The spatial arrangements of secondary valencies give definite geometrical shapes like
octahedral, tetrahedral , square planar shapes to coordination compounds.
Example: consider [Co(NH3)6]Cl3 complex. Central metal ion = Co3+ ,
primary valency = +3 satisfied by 3 Cl– ions
secondary valency = 6 satisfied by 6 NH3 molecules. It has octahedral shape
Limitations of Werner's Theory : This theory cannot explain ,
a. why only certain elements can form coordination compounds.
b. why the secondary valences have directional properties.
c. why coordination compounds have characteristic magnetic and optical properties.

Question: On the basis of the Formula Moles of AgCl precipitated per mole of
following observations made with the compounds with excess AgNO3
aqueous solutions, assign (i) PdCl2. 4NH3 2
secondary valences to metals in (ii) NiCl2. 6H2O 2
the following compounds: (iii) PtCl4. 2HCl 0
(iv) CoCl3. 4NH3 1
(v) PtCl2. 2NH3 0
Answer : ---half page ---
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IUPAC RULES FOR NAMING OF COORDINATION COMPOUND
The names of ligands surrounding the central metal ion are listed as prefixes along with appropriate multipliers.
The following rules are used when naming coordination compounds:

(i) The cation is named first in both positively and negatively charged coordination entities.
(ii) The ligands are named in an alphabetical order before the name of the central atom / ion.
(This procedure is reversed from writing formula).
(iii) Names of the anionic ligands end in –o, those of neutral and cationic ligands are the same
except aqua for H2O, ammine for NH3, carbonyl for CO and nitrosyl for NO , pyridyl for
C5H5N. These are placed within enclosing marks ( ).
(iv) Prefixes mono, di, tri, etc., are used to indicate the number of the individual ligands in the
coordination entity. When the names of the ligands include a numerical prefix, then the
terms, bis, tris, tetrakis are used, the ligand to which they refer being placed in parentheses.
For example, [ NiCl2(PPh3)2 ] is named as dichlorobis(triphenylphosphine)nickel(II).
(v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by
Roman numeral in parenthesis.
(vi) If the complex ion is a cation, the metal is named same as the element.
For example, In complex cation [Co(NH 3)6]3+ , Co is named as cobalt.
In complex cation [Pt (NH3)4]2+ , Pt is named as platinum.
If the complex ion is an anion, the name of the metal ends with the suffix – ate.
For example, In complex anion [ Co F6] 3– , Co is named as cobaltate.
In complex anion [Fe(CN)6]4– , Fe is named as ferrate (latin name).
(Similarly , platinate , argentate , hydrarginate, nickelate , chromate , aurate )
(vii) The neutral complex molecule is named similar to that of the complex cation.

Note : The names of negative ligands end with -o . Examples:

CN- cyano or cyanido , F- fluorido , Cl- chlorido , Br- bromido , I- iodido , OH- hydroxo or hydroxido ,
CO32- carbonato , SO42- sulphato , CH3-COO- acetato , C2O42- oxalato , NO2- with donor atom N is
nitrito-N- , NO2- with donor atom O is nitrito-O-, SCN- is thiocyanato , NCS- is isothiocyanato

Set 1. Give the IUPAC names of following

Answer:

Set 2. Give the IUPAC names of following

Answer:
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RULES FOR WRITING FORMULA OF COORDINATION COMPOUND
(i) The central atom is listed first.
(ii) The ligands are then listed in alphabetical order. The placement of a ligand in the list does
not depend on its charge.
(iii) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the first letter of the
abbreviation determines the position of the ligand in the alphabetical order.
(iv) The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets.
When ligands are polyatomic, their formulas are enclosed in parentheses. Ligand abbreviations are also
enclosed in parentheses.
(v) There should be no space between the ligands and the metal within a coordination sphere.
(vi) When the formula of a charged coordination entity is to be written without that of the counter ion, charge is
indicated outside square brackets as a right superscript- number before the sign.
(vii) The charge of the cation(s) is balanced by the charge of the anion(s).

Set 3. Give the Formula of the following

Answers:

Set 4. Give the formula of the following

Answers:

Set 5. Give the IUPAC names of following

Set 6. Give the IUPAC names of following

Set 7. Give the formula of the following

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Practice Questions
Set 8. Name the following compounds ( First find the charge on central metal and then proceed to name )
Compound Charge Name
1. [ Co(NH3)6 ] Cl3 Co =+3 Hexaamminecobalt(III) chloride
2. K3 [ CoF6 ] Co =+3 Potassium hexafluoridocobaltate(III)
3. [Cu(NH3)4 ] SO4 Cu =+3 Tetraamminecopper(II) sulphate
4. Ba [ Cu(OH)4 ] Cu =+3 Barium tetrahydroxocuprate(II)
5. K4 [ Fe(CN)6 ] Fe =+2 Potassium hexacyanoferrate(II)
6. K3 [ Fe(CN)6 ] Fe =+3 Potassium hexacyanoferrate(III)
7. [ Pt(NH3)4 ] Cl2 Pt =+2 Tetraammineplatinum(II) chloride
8. K2 [ Pt Cl6 ] Pt =+4 Potassium hexachloridoplatinate(IV)
9. [ Cr(H2O)6 ]Br3 Cr =+3 Hexaaquachromium(III) bromide
10. Na3 [ CrCl6 ] Cr =+3 Sodium hexachloridochromate(III)
11. [ Co(NH3)5SO4]Br Co =+3
12. [ Co(NH3)5Br]SO4 Co =+3
13. Na3 [ Fe(C2O4)3 ] Fe =+3
14. K3[ Cr(ox)3] Cr =+3
15. [ Ag(NH3)2 ] Cl Ag=+1
16. K2 [ Hg I4 ] Hg =+2
17. [ Ni(CO)4 ] Ni = 0
18. [NiCl2(H2O)4] Ni =+2
19. K2 [ Ni(CN)4 ] Ni =+2
20. [ Cr(NH3)3(H2O)3 ]Cl3 Cr =+3
21. [ CoCl2 (en)2 ]Cl Co =+3
22. Na [ Au(CN)2 ] Au=+1
23. K2[ PdBr4 ] Pd =+2
24. [ Pt(NH3)2Cl(NO2) ] Pt =+2
25. [ Co(NH3)5(CO3) ]Cl Co =+3
26. [ Co(en)3 ]Cl3 Co =+3
27. [ NiCl2(PPh3)2 ] Ni =+2
28. [ Pt(NH3)2Cl(NH2CH3) ]Cl Pt =+2
29. [Co(H2NCH2CH2NH2)3]2 (SO4)3 Co =+3
30. [ Ag (NH3)2] [ Ag (CN)2 ] Ag=+1, +1
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VALENCE BOND THEORY: Salient features
*According to VBT , Metal to Ligand bond is purely co-valent .
*Each ligand donates at least one electron pair to central metal ion.
*The central metal ion prepares vacant orbitals to accept electron pairs from ligands.
*The number of vacant orbitals is equal to coordination number or secondary valency.
*Vacant orbitals undergo hybridisation to attain stability. In this process [ (n-1) d , n s & n p ]
orbitals are mixed or [ n s , n p , n d ] orbitals are mixed to form equal energy orbitals.
*The type of hybridisation decides the shape of the complex.

Note1 : * For metal ions with up to three electrons in d orbitals, Ti 3+ (d1); V3+ (d2 ) ; Cr3+ (d3 ); two vacant d
orbitals are available for octahedral hybridisation with 4s and 4p orbitals. The magnetic behaviour of these
free ions and their coordination entities is similar.

Note2. * When more than three 3d electrons are present, the required pair of 3d orbitals for octahedral
hybridisation is not directly available( Hund’s rule). Hence for d4 (Cr 2+ , Mn3+ ), d5 (Mn2+ , Fe3+ ), d6 (Fe2+ ,
Co3+ ) cases, two d orbitals results only by pairing of 3d electrons. Two, one and zero unpaired electrons are
present respectively.

Examples: * [ Mn (CN)6]3– , [Fe(CN)6]3– and [Co(C2O4)3]3– are inner orbital complexes with d2sp3
hybridisation. The first two complexes are paramagnetic and the last one isdiamagnetic.

* [MnCl6]3– , [FeF6]3– and [CoF6]3– are outer orbital complexes with sp3d2 hybridisation and are
paramagnetic with four, five and four unpaired electrons respectively.

Limitations of Valence Bond Theory:

1. This theory does not explain the colour exhibited ( spectral properties ) of complexes.
2. It can't exactly predict the tetrahedral and square planar structures of 4-coordinate complexes.
3. It does not distinguish between weak and strong ligands.
4. It does not give a quantitative interpretation of the thermodynamic stabilities of complexes.

Inner orbital complexes: When ligands NH3 , CN- (strong field ligands) approach central metal ion,
electrons are paired . Hence Inner (n-1) d orbitals are used for bonding. Such complexes are called Inner orbital
complexes. They are Low Spin or Spin paired complexes.
Example : [ Co(NH3)6 ]3+ or [ Co(NH3)6 ]Cl3
Outer orbital complexes: When ligands F- , Cl- ( weak field ligands ) approach central metal ion, electrons
are not paired. Hence Outer n d orbitals are used for bonding. Such complexes are called Outer orbital
complexes. They are High Spin or Spin free complexes.
Example : [ CoF6 ]3– or K3 [ CoF6 ]
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Applications of VBT to explain formation of some complexes

Question1 . Explain formation, shape & magnetic properties of [ Co(NH 3)6 ]3+ using VBT
[ Explain Inner orbital complex with a suitable example ]

Answer: Consider the complex [ Co(NH3)6 ]3+ . Coordination number is 6.

Here, Central metal ion : Co3+ , Ligands : 6 NH3 molecules ( strong field )
Cobalt atom has 27 electrons : Co [ Ar ]18 3d7 4s2 4p0
[ 27]
Co3+ ion has 24 electrons : Co3+ [ Ar ]18 3d6 4s0 4p0
[ 24 ]
As 6 NH3 ligands approach(Strong Field), electrons are paired and 2 vacant d orbitals are formed. Inner 3d, 4s
and 4p orbitals are mixed. d2sp3 hybridisation takes place and SIX hybrid orbitals are formed.
SIX NH3 ligands donate one electron pair each to these hybrid orbitals.
Co3+ [ Ar ]18 3d6 4s0 4p0
[ 24 ]

d 2sp3 hybridisation

electron pairs donated from 6 NH 3 ligands

Conclusion: * This complex has Octahedral shape due to d 2sp3 hybridisation.
* Unpaired electrons are absent. Hence it is Diamagnetic and a Low spin complex.
* Inner (n-1) d or 3d orbitals are used and hence it is called Inner Orbital complex.

Question2. Explain formation, shape & magnetic properties of [CoF6 ]3– using VBT
[ Explain Outer orbital complex with a suitable example ]

Answer: Consider the complex [ CoF6 ]3– . Coordination number is 6.

Here, Central metal ion : Co3+ , Ligands : 6 F– ions ( weak field )
Cobalt atom has 27 electrons : Co [ Ar ]18 3d7 4s2 4p0 4d0
[ 27 ]
Co3+ ion has 24 electrons : Co3+ [ Ar ]18 3d6 4s0 4p0 4d0
[ 24 ]
–
As 6 F ligands approach(Weak Field), electrons are not paired in d orbital . 4s , 4p and Outer 4d orbitals are
mixed. sp3d2 hybridisation takes place and SIX hybrid orbitals are formed.
SIX F– ligands donate one electron pair each to these hybrid orbitals.
Co3+ [ Ar ]18 3d6 4s0 4p0 4d0
[ 24 ]

sp3d2 hybridisation

electron pairs donated from 6 F – ligands

Conclusion: * This complex has Octahedral shape due to sp 3d2 hybridisation.
* Four unpaired electrons are present. Hence it is Paramagnetic and a High spin complex.
* Outer n d or 4d orbitals are used and hence it is called Outer Orbital complex.
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Question 3 . Explain formation, shape & magnetic properties of [ Ni(CN)4 ] 2- using VBT
[ Ni(CN)4 ] 2- is square planar and diamagnetic . Explain.

Answer: Consider the complex [ Ni(CN)4 ] 2- . Coordination number is 4.

Here, Central metal ion : Ni2+ , Ligands : 4 CN- ions ( strong field )
Nickel atom has 28 electrons : Ni [ Ar ]18 3d8 4s2 4p0
[ 28]
Ni2+ ion has 26 electrons : Ni2+ [ Ar ]18 3d8 4s0 4p0
[ 26 ]
As 4 CN- ligands approach(Strong Field), electrons are paired and one vacant d orbital is formed. 3d, 4s and 4p
orbitals are mixed. d sp 2 hybridisation takes place and FOUR hybrid orbitals are formed.
FOUR CN- ligands donate one electron pair each to these hybrid orbitals.
Ni2+ [ Ar ]18 3d8 4s0 4p0

[ 26 ]

d sp 2 hybridisation

electron pairs donated from 4 CN- ligands

Conclusion: * This complex has Square planar shape due to d sp 2 hybridisation.
* Unpaired electrons are absent. Hence it is Diamagnetic .

Question 4 . Explain formation, shape & magnetic properties of [ Ni Cl 4 ] 2- using VBT

[ Ni(Cl4 ] 2- is tetrahedral and paramagnetic . Explain.

Answer: Consider the complex [ Ni Cl4 ] 2- . Coordination number is 4.

Here, Central metal ion : Ni2+ , Ligands : 4 Cl- ions ( weak field )
Nickel atom has 28 electrons : Ni [ Ar ]18 3d 8 4s2 4p0
[ 28]
Ni2+ ion has 26 electrons : Ni2+ [ Ar ]18 3d 8 4s0 4p0
[ 26 ]
As 4 Cl- ligands approach(Weak Field), electrons are not paired and vacant d orbital is not formed. 4s and 4p
orbitals are mixed. sp3 hybridisation takes place and FOUR hybrid orbitals are formed.
FOUR Cl- ligands donate one electron pair each to these hybrid orbitals.
Ni2+ [ Ar ]18 3d 8 4s0 4p0
[ 26 ]

sp 3 hybridisation

electron pairs donated from 4 Cl- ligands

Conclusion: * This complex has Tetrahedral shape due to sp 3 hybridisation.

* Two unpaired electrons are present. Hence it is Paramagnetic.
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CRYSTAL FIELD THEORY
[ Crystal Field Splitting , t2g and eg Sets ]
According to CFT,
1. The bond between Metal and Ligand bond is purely ionic. There is electrostatic force of attraction between
central Metal ion and Ligand.

2. Ligands act as point charges in case of negative ions ( Cl-, CN-) & dipoles in case of molecules(NH 3, H2O).

3. The d orbitals of central metal ion are degenerate. This means, the five d-orbitals d xy , dyz , dxz , dx2-y2, dz2 have
same energy. They form a spherically symmetrical field of negative charges. But when Ligands approach, the
symmetry of field is destroyed and d-orbitals split into two sets namely eg Set and t2g Set. This is known as
Crystal Field Splitting.
" Crystal Field Splitting is the separation of degenerate d-orbitals into two sets due to
Octahedral or Tetrahedral geometrical Field produced by Ligands "

4. The type of splitting depends on nature of the crystal field like Octahedral or Tetrahedral field.
(i) Crystal Field Splitting in Octahedral Field (ii) Crystal Field Splitting in Terahedral Field
( when 6 ligands approach) ( when 4 ligands approach)

The d-orbitals split into two sets
Set1: t2g Set orbitals .
The energy of three orbitals dxy , dyz , dxz are lowered
and they are said to be stabilised.
Set2: eg Set orbitals .
The energy of two orbitals dx2-y2, dz2 are increased
and they are said to be excited.
The d-orbitals split into two sets
Set1: t2 Set orbitals .
The energy of three orbitals dxy , dyz , dxz are
increased and they are said to be excited.
Set2: e Set orbitals .
The energy of two orbitals dx2-y2, dz2 are lowered and
they are said to be stabilised.

Or eg set Or

t2 set
Degenerate d-orbitals Degenerate d-orbitals

e set
t2g set
The energy separation is denoted by Δo. The energy separation is denoted by Δt.
* Energy of two eg orbitals will increase by (3/5) Δo
* Energy of two e orbitals will decrease by (3/5)Δt
* Energy of three t2g will decrease by (2/5)Δo.
* Energy of three t2 will increase by (2/5)Δt.

Note: For the same metal, ligands and metal-ligand distances, it can be shown that Δt = (4/9) Δo
(In Tetrahedral Field , ' g ' is not used. only e set and t2 set symbols are used )
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Spectrochemical series: [ Strong Field and Weak Field ligands]
The extent of Crystal Field Splitting [Δo ] depends on the strength of field produced by the ligands and charge
on metal ion.

" Spectrochemical series is the arrangement of ligands in increasing order their field strength "

I–< Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4- < NH3 < en < CN- < CO
weak field ligands strong field ligands

* Strong Field ligand produces a Strong Field and causes large d-orbital splitting. Eg: NH 3, en , CN- , CO
* Weak Field ligand produces a Weak Field and causes small d-orbital splitting. Eg: F-, Cl-, SCN-, Br-, I-

Applications of Crystal Field Theory

Study of d4 system in Octahedral Field :

Consider d4 configuration of a complex in Octahedral Field. There are two possibilities:

Case(i) If Separation energy is less than Paring energy [Δo ] < [ P ]:

If Energy of Crystal Field Splitting Δo is less than the Pairing energy [ P ], then Fourth electron jumps to
higher eg Set.
The electronic configuration is d4 = t2g3 eg1
This results in a high spin complex. Such Ligands where [Δo ] < [ P ] are known as Weak Field Ligands .

eg 1
d4

t2g3
Case(ii) If Separation energy is more than Paring energy [Δo ] > [ P ]:

If Energy of Crystal Field Splitting Δo is more than the Pairing energy [ P ], then Fourth electron pairs with a
t2g electron.
The electronic configuration is d4 = t2g4 eg0
This results in a low spin complex. Such Ligands where [Δo ] > [ P ] are known as Strong Field Ligands .

eg 0
d4

t2g4
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ISOMERISM IN COORDINATION COMPOUNDS
Complexes show two types of Isomerism: I Structural isomerism II Stereoisomerism

I Study of Structural isomerism : These are the coordination compounds having same molecular
formula and composition but differ in bonding.

(i) Linkage isomerism : These are the isomers which differ in linkage between donor atom of Ligand and
central metal ion. This isomerism arises due to ambi-dentate ligands like NO 2- , SCN-
Example : [Co(NH3)5(NO2)]Cl2 .... donor atom is N
and [Co(NH3)5(ONO)]Cl2.... donor atom is O

(ii) Ionisation isomerism : These are the isomers which differ in counter ions formed in solution. This
isomerism arises due to exchange of counter ion with a ligand.
Example: [Co(NH3)5SO4]Br .... gives free Br- ion in solution.
and [Co(NH 3)5Br]SO4 .... gives free SO42- ion in solution.

(iii) Solvate isomerism : These are the isomers which differ in number of Solvent(water) molecules binding to
metal ion as ligand. This isomerism arises when water is present as solvent. Water can act as ligand also.
Example: [Cr(H2O)6 ] Cl3 ....6H2O ligands
and [Cr(H2O)5 Cl ] Cl2.H2O ....5H2O ligands

(iv) Coordination isomerism : These are the isomers which differ in cationic and anionic coordination entities.
This type of isomerism arises from the interchange of ligands between cationic and anionic entities .
Example: [Co(NH3)6] [Cr(CN)6] .... NH3 bound to Co3+ and CN– bound to Cr3+
and [Cr(NH3)6] [Co(CN)6]..... NH3 bound to Cr3+ and CN– bound to Co3+

II Study of Stereoisomerism : These are the coordination compounds having same molecular
formula and composition but differ in spatial arrangement.

(i) Geometrical isomerism : These are the isomers which differ in geometrical arrangements of ligands. This
isomerism arises in heteroleptic complexes of coordination numbers 4 and 6. Example1: Cis-[Co(NH 3)4Cl2]+
and trans-[Co(NH3)4Cl2]+

Example2: Cis-[Pt(NH3)2Cl2] and trans-[Pt(NH3)2Cl2]

(ii) Optical isomerism : These are the optically active isomers which rotate plane polarised light to the same
extent in opposite directions. They are Chiral molecules whose structures are non-superimposable mirror
images. The two forms are called dextro (d) and laevo (l) depending on the direction they rotate the plane of
polarised light.
Example: dextro or d [Co(en)3 ] 3+ and laevo or l [Co(en)3 ] 3+
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Facial and Meridional Isomers : This is a special case of Geometrical isomerism occurs in octahedral
coordination entities of the type [M a3 b3] like [Co(NH3)3(NO2)3].
(i) If three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral face then
it is Facial isomer(fac).
(ii) If the positions are around the meridian of the octahedron then it is meridional (mer) isomer.

Colours of Complexes
Complex compounds show wide range of colours. According to Crystal Field theory , colour of the
coordination compounds is due to d-d transition of the electron. Electronic transitions takes place between d-
orbitals of t2g set and eg set by interacting with Visible light. Visible light is partly absorbed and remaining is
reflected. The reflected light gives colour to complex. Absorbed colour and reflected colour are called
complementary colours.
List of Absorbed colour and complementary colours
Complex Wavelength of Colour of Colour of
absorbed light absorbed light complex

Example: If light corresponding to the energy of yellow-green region is absorbed by the complex, it would
excite the electron from t2g level to the eg level . (t2g1 eg0 → t2g0 eg1). Hence complex appears violet in colour.

Metal carbonyls
Metal carbonyls are the homoleptic complexes in which Carbonyl ligand ( CO ) is joined to transition metal
atom by coordinate bond. The oxidation state of Metal is zero. There are two types of Metal carbonyls.

Type(i) Mononuclear metal carbonyls: In these complexes , only one metal atom is present per molecule.

Tetracarbonylnickel(0) Pentacarbonyliron(0) Hexacarbonylchromium(0)

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]
Tetrahedral shape Trigonal bipyramidal shape Octahedral shape
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Type(ii) Polynuclear metal carbonyls: In these complexes , two or more metal atoms are present per molecule.

Decacarbonyldimanganese(0) Octacarbonyldicobalt(0)
[Mn2(CO)10] [Co2(CO)8]

* Two square pyramidal units of Mn(CO)5 are joined.

Bonding Metal carbonyls

The Metal-Carbon [ M- C ] bond in metal carbonyls possess

both s( sigma) and p (pi) character.

* The M–C σ bond is formed when Carbonyl ligand (CO)

donates one pair of electrons to the vacant orbital of Metal.

*The M–C π bond is formed when filled d orbital of metal

donates one pair of electrons to the vacant anti bonding π*
orbital of carbon monoxide.

Result: This Mutual Metal to Ligand bonding creates a

synergic effect which strengthens the bond between CO and
the Metal.
Stability of Complexes

The stability of a complex in solution indicates the degree of association between the two species ( Metal and
Ligands) in equilibrium. The magnitude of the equilibrium constant for the formation of complex expresses the
stability. Consider the reaction of the type: M + 4 L ═ ML4
Metal Ligand Complex
Larger the stability constant, higher is the proportion of ML 4 that exists in solution.
(Free metal ions rarely exist in the solution. Metal M is usually surrounded by solvent molecules which
compete with the ligand molecules L. For simplicity, we generally ignore these solvent molecules )
We can write four stability constants for four steps:

where K1, K2, K3, K4 are referred to as stepwise stability constants. We can write the overall stability constant as
M + 4 L ═ ML4 β4 = [ML4] / [M ][L]4

The stepwise and overall stability constant are related as follows:

β4 = K1 × K2 × K3 × K4 or more generally , βn = K1 × K2 × K3 × K4 ...... × Kn

For example , consider formation of [Cu(NH3)4]2+ complex : Cu2+ + 4 NH3 ═ [ Cu(NH3)42+ ]

The overall stability complex is β4 = [ Cu(NH3)42+ ] / [Cu2+ ] [NH3]4
Stability complex is also called Formation constant.
The reciprocal of Stability constant is called instability constant or dissociation constant.