COORDINATION COMPOUND – REVISION NOTE (AJC)

➢ chlorophyll (Mg - complex) in plants and haemoglobin (Fe- complex)

HOMOLEPTIC COMPLEX: When the coordination centre is bound to only one type of ligand group. Eg: [Cu(CN)4]3-.
HETEROLEPTIC COMPLEX: When the central atom is bound to many different types of ligands, Eg:[Co(NH3)4Cl2]+.
UNIDENTATE LIGANDS: The ligands which only have one atom that can bind to the coordination centre. Eg: NH3, Cl–, H2O
BIDENTATE LIGANDS: Ligands which have the ability to bind to the central atom via two separate donor atoms. Eg:
ethane-1,2-diamine, Oxalate ion
POLYDENTATE LIGANDS: ligands have many donor atoms that can bind to the coordination centre. Eg: EDTA4-(hexa dentate)
CHELATE LIGAND: When a polydentate ligand attaches to the central metal atom through two or more donor atoms at a time.
Eg: ethane-1,2-diamine, Oxalate ion
AMBIDENTATE LIGAND: Some ligands have the ability to bind to the central atom via the atoms of two different elements.
Eg: SCN-, NO2
NOMENCLATURE:

ISOMERS: Two or more compounds that have the same chemical formula but a different arrangement of atoms.
 COORDINATION COMPOUND – REVISION NOTE (AJC)
GEOMETRIC ISOMERISM: This type of isomerism is common in heteroleptic complexes. It arises due to the different
possible geometric arrangements of the ligands.

OPTICAL ISOMERISM: This type of isomerism arises in chiral molecules. Isomers are mirror images of each other and are
non-superimposable.

LINKAGE ISOMERISM: This type of isomerism is found in complexes that contain ambidentate ligands.
[Co(NH3)5 (NO2)]Cl2 and [Co(NH3)5 (ONO)Cl2
COORDINATION ISOMERISM: when the ligands are interchanged between cationic and anionic entities of differnet metal
ions present in the complex. [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
IONIZATION ISOMERISM: when a counter ion replaces a ligand within the coordination sphere. Thus, complexes that have
the same composition, but furnish different ions when dissolved in water. Co(NH3)5SO4)Br and Co(NH3)5Br]SO4.
SOLVATE ISOMERISM: Solvate isomers differ by whether or not the solvent molecule is directly bonded to the metal ion or
merely present as a free solvent molecule in the crystal lattice. Cr[H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2⋅H2O and [Cr(H2O)5Cl2]Cl⋅2H2O
POSTULATES OF WERNER’S THEORY
1. The central metal atom in the coordination compound exhibits two types of valency, namely, primary and secondary valencies.
2. Primary linkages are ionizable and are
satisfied by the negative ions.
3. Secondary linkages are non-ionizable.
These are satisfied by negative ions. Also,
the secondary valence is fixed for any
metal and is equal to its coordination
number.
4. The ions bounded by the secondary
linkages to the metal exhibit characteristic
spatial arrangements corresponding to
different coordination numbers.
SPECTRO CHEMICAL SERIES: The series of increasing order of field strength of ligands
I– < Br– < SCN– < Cl– < S-2 < F– < OH– < C2O-24 < H2O < NCS− < (EDTA)-4 < NH3 < en < CN < CO
VALENCE BOND THEORY(VBT) was developed by Linus Pauling. The main assumption made by him was that the metal-
ligand bonds are formed by the donating of an electron pair by the ligand to the metal and thus form a coordinate bond
between the metal and ligand.

1. [Co(CN)6]3- → hexacyanido cobaltate (III) ion

• Oxidation sate of metal ion : X+ (-1 × 6 ) = -3 → X = +3
 COORDINATION COMPOUND – REVISION NOTE (AJC)

• Co → 3d74s2 Co3+ → 3d6

• CN- is a strong field ligand. So, pairing will happen. → d2sp3 hybridization
• d sp hybridization, octahedral shape, inner orbital complex, diamagnetic behaviour, low spin complex.
2 3

2. [Fe(F)6]3- → hexafluorido ferrate (III) ion

• Oxidation state of metal ion : X + ( -1 × 6 ) = -3 → X = +3
• Fe → 3d64s2 Fe3+ → 3d5
• F- is a weak field ligand. So, no pairing will happen. → sp3d2 hybridization.
• sp3d2 hybridization, octahedral shape, outer orbital complex, paramagnetic behaviour, high spin complex.
3. [NiCl4]2- → tetrachlorido nickelate (II) ion
• Oxidation state of metal ion : X + ( -1 × 4 ) = -2 → X = +2
• Ni → 3d84s2 Ni2+ → 3d8
• Cl- is a weak field ligand. So, no pairing will happen. → sp3 hybridization
• Sp3 hybridization, tetrahedral shape, paramagnetic behaviour, high spin complex
4. [Ni(CN)4]2- → tetracyanido nickelate (II) ion
• Oxidation number of metal ion : X + ( -1 × 4 ) = -2 → X = +2
• Ni → 3d84s2 Ni2+ → 3d8
• CN- is a strong field ligand. So, pairing will happen. → dsp2 hybridization
• dsp2 hybridization, square plannar shape, diamagnetic behaviour, low spin complex.
LIMITATIONS OF VALENCE BOND THEORY
➢ It could not explain the nature of ligands.
➢ It could not explain why the pairing of electrons occurs in the presence of strong ligands.
➢ It could not explain the colour and electronic spectra of complexes.
CRYSTAL FIELD THEORY: When transition metals are not bonded to any ligand,
their d orbitals degenerate that is they have the same energy. When they start
bonding with other ligands, due to different symmetries of the d orbitals and the
inductive effect of the ligands on the electrons, the d orbitals split apart and
become non-degenerate.
1. CFT IN OCTAHEDRAL COMPLEX: repulsion is experienced more in the case of dx2-
y2 and dz2 orbitals as they point towards the axes along the direction of the ligand.
Hence, they have higher energy than average energy in the spherical crystal field.
The difference between the energy of t2g and eg level is called crystal field splitting
energy denoted by “Δo”

2. CFT IN TETRAHEDRAL COMPLEX: repulsion is experienced more in the case of dxy,

dyz, and dxz orbitals as they point in between the axes along the direction of the
ligand. Hence, they have higher energy than average energy in the spherical
crystal field. The difference between the energy of e and t2 level is called crystal
field splitting energy denoted by “ΔT”

3. RELATION BETWEEN ΔO AND ΔT:

4. CFT BASED ELECTRONIC CONFIGURATION: Δo > P → pairing is possible Δo < P → pairing is not possible
Eg: d4 → Δo > P : t2g4eg0 Δo < P : t2g3eg1 d5→ Δo > P : t2g5eg0 Δo < P : t2g3eg2 d6 → Δo > P : t2g6eg0 Δo < P : t2g4eg2

METAL CARBONYLS - ORGANOMETALLICS : In a metal carbonyl, the metal-carbon bond possesses both the σ and π
character. The bond between the carbonyl molecule and the metal is further strengthened by the synergic effect produced
by the metal-ligand bond.
 COORDINATION COMPOUND – REVISION NOTE (AJC)
1. Give the formulae of the following compounds :
(a) Potassium tetrahydroxidozincate (II) → ANS) K2[Zn(OH)4] → K = +1 , Zn = +2 , OH = -1
(b) Hexaammineplatinum (IV) chloride → ANS) [Pt(NH3)6]Cl4 → Pt = +4 , NH3 = 0 , Cl = -1
(c) Potassium trioxalatoaluminate (III) → ANS) K3[Al(C2O4)3] → K = +1 , Al = +3 , C2O4 = -2
(d) Tetraammineaquachloridocobalt (III) chloride → ANS) [Co(NH3)4(H2O)Cl]Cl2 → Co = +3 , NH3 = 0 , H2O = 0 , Cl = -
(e) Pentaamminecarbonatocobalt (III) chloride → ANS) [Co(NH3)5(CO3)]Cl → Co = +3 , NH3 = 0 , CO3 = -2 , Cl = -1
(f) Potassium tetracyanidonickelate (II) → ANS) K2[Ni(CN)4] → K = +1 , Ni = +2 , CN = -1
(g) Dichloridobis(ethane-1,2-diamine)cobalt(III) → ANS) [CoCl2(en)2]+ → Co = +3 , Cl = -1 , en = 0
(h) Tetracarbonylnickel(0) → ANS) [Ni(CO)4] → In presence of CO the metal will have 0 oxidation state.
(i) Hexaamminecobalt(III) sulphate → ANS) [Co(NH3)6]2 (SO4)3 →Co = +3 , NH3 = 0 , SO4 = -2
(j) Potassium trioxalatochromate(III) → ANS) K3 [Cr(C2O4)3] → K = +1 , Cr = +3 , C2O4 = -2
(k) Tetraamminediaquacobalt(III) chloride → ANS) [Co(NH3)4(H2O)2]Cl3 → Co= +3 , NH3 = 0, H2O = 0 , Cl = -1
(l) Dibromidobis(ethane-1,2-diamine)platinum(IV) nitrate → ANS) [Pt(Br)2(en)2](NO3)2 → Pt = +4, Br= -1 , en = 0 ,NO3 =-1
(m) Hexaaquamanganese(II) sulphate → ANS) [Mn(H2O)6]SO4 → Mn = +2, H2O= 0 , SO4 = -2
(n) Iron(III) hexacyanoferrate(II)→ ANS) Fe4 [Fe(CN)6]3 → Fe= +2,+3 , CN= -1
2. Give the IUPAC name and electronic configuration of central metal atom in terms of t2g and eg of K4[Mn(CN)6]?
ANS) K4[Mn(CN)6] →( 1 × 4 ) + X + ( -1 × 6) = 0 → X = +2 → Mn = 3d54s2 , Mn2+ = 3d5 → CN- is a SFL so, pairing happen → t2g5eg0
3. What is meant by ‘Chelate effect’? Give an example. ANS) When a chelate ligand attaches to the metal ion in a manner that
forms a ring, then the complex attain extra stability. Eg: [Pt(en)Cl2] is more stable than [Pt(H20)Cl2] , en is a chelate ligand.
4. Write the hybridisation and magnetic characters of the following complexes : (i) [Fe(CN)6] 4– (ii) [CoF6] 3– (iii) [Ni(CO)4]
ANS) [Fe(CN)6] 4– → oxidation sate = X + (-1 × 6) = -4 → X= +2. → Fe = 3d64s2 , Fe2+ = 3d6 → CN- is a SFL so, pairing will
happens → → hybridization= d2sp3, octahedral shape, inner orbital complex, diamagnetic behaviour,
low spin complex.
[CoF6] 3–→ oxidation state = X + (-1 × 6) = -3 → X = +3 → Co = 3d74s2 , Co3+= 3d6 → F- is a WFL so, no pairing is possible →

→ hybridization= sp3d2, octahedral shape, outer orbital complex, paramagnetic behaviour, high
spin complex.
[Ni(CO)4] → oxidation state = 0 ( ligand is CO) → Ni = 3d84s2 → CO is a SFL so, pairing happen
→hybridization = sp3 , tetrahedral shape, diamagnetic behaviour, low spin complex.
5. What type of isomerism is shown by i) [Co(NH3)5 NO2] Cl2 ANS) linkage isomerism (NO2 is a ambidentate ligand) ii) [Co(en)2Cl2]2+
ANS) geometric and optical (cis form only) isomerism.
6. How can you show that complexes [Co(NH3)5 Cl] SO4 and [Co(NH3)5 SO4] Cl are ionization isomers ?
ANS) [Co(NH3)5Cl] SO4 gives white precipitate with BaCl2 solution while [Co(NH3)5SO4 ] Cl does not respond to this test. On
contrary to this [Co(NH3)5SO4] Cl gives white precipitate with silver nitrate solution while [Co(NH3)5Cl] SO4 does not respond
to this test.
7. Discuss the nature of bonding in metal carbonyls?
8. Write the IUPAC name and hybridisation of the following complexes :
a) [Ni(CO)4] → ANS) Tertacarbonyl nickel(0) → Ni= 0
b) [CoF6] 3– → ANS) Hexafluorido cobaltate(III) ion → F= -1 , Co = +3,
c) [Co(NH3)6] 3+ →ANS) Hexaammine cobalt(III) ion → NH3 = 0 , Co= +3
d) [NiCl4] 2– → ANS) Tetrachlorido nickelate(II) ion → Cl = -1 , Ni = +2
e) [Fe(CN)6] 3– → ANS) Hexacyanido ferrate(III) ion → CN = -1 , Fe = +3
f) [Pt(en)2Cl2] → ANS) Dichloridobis(ethane-1,2-diamine) platinum(II) → Cl = -1 , en = 0 , Pt = +2
g) [Cr(NH3)4Cl2]+ → ANS) Tetraamminedichlorido chromium(III) ion → NH3 = 0 , Cl = -1 , Cr = +3
h) [Co(NH3)5(ONO)]Cl2 → ANS) Pentaamminenitrito-O-cobalt(III) chloride
i) [Co(en)2(H2O)(CN)]2+ → ANS) Aquacyanidobis(ethane- 1, 2 diamine)cobalt(III) ion
j) Na[Au(CN)2] → ANS) Sodium dicyanidoaurate(I)
k) [Pt(NH3)4Cl(NO2)]SO4 → ANS) Tetraamminechloridonitrito-N-platinum(IV) sulphate →Pt=+4, NH3=0, Cl=-1, NO2=-1, SO4=-2
9. Out of Cis–[Pt(en)2Cl2] 2+ and Trans–[Pt(en2)Cl2] 2+, which one isoptically active ?
ANS) cis - [Pt(en)2Cl2]2+ → If chelate ligand is present then only the cis form is having optical isomerism ie, optically active.
10. Define ambidient nucleophile with an example? ANS) nucleophiles having two nucleophilic sites. ambident nucleophiles have
 COORDINATION COMPOUND – REVISION NOTE (AJC)

two sites through which they can attack. Eg: NO2, SCN-
11. Out of [CoF6] 3– and [Co(en)3] 3+, which one complex is (i) paramagnetic (ii) more stable (iii) inner orbital complex
ANS) Co→ 3d74s2 Co3+ → 3d6 i) [CoF6] 3– (F- is a WFL), ii) [Co(en)3] 3+ (chelate effect) iii) [Co(en)3] 3+ (en is a SFL)
12. Write the hybridization and magnetic character of following complexes : (i) [Fe(H2O)6] 2+ (ii) [Fe(CO)5] iii) [Fe(CN)6] 4–
iv) [Co(C2O4)3] 3– V) 𝐊𝟒[𝐌𝐧(𝐂𝐍)𝟔] (vi) [𝑪𝒐(𝑵𝑯𝟑)𝟓𝑪𝒍]𝑪l2
13. Write the electronic configuration of d6 and d5 on the basis of crystal field theory when (i) o < P and (ii) o > P
14. Although both [NiCl4] 2– and [Ni(CO)4] have sp3 hybridisation yet [NiCl4] 2– is paramagnetic and [Ni(CO)4] is diamagnetic?
ANS) Cl– is WFL and it does not cause the pairing of unpaired 3d electron. Hence [NiCl4]–2 is paramagnetic.
[Ni(CO)4] Ni is in zero oxidation state i.e. it has a configuration of 3d84s2 . But CO is SFL. It causes the pairing of unpaired 3d
electron. Also it causes the 4s electrons to shift to the 3d orbital, thereby giving rise to sp3 hybridization. Since no unpaired
electrons are present in this Case, [Ni(CO)4] is diamagnetic.
15. When a coordination compound CrCl3. 6H2O is mixed with AgNO3, two moles of AgCl are precipitated per mole of the
compound. What is the structural formula of the coordination compound?
ANS) [Cr(Cl)(H20)5]Cl2. H2O
16. Arrange the following in increasing order of crystal field splitting energy : [Cr(CN)6] 3– , [Cr(NH3)6] 3+, [CrCl6] 3–
ANS) CFSE is higher when the complex contains strong field ligand. Thus, crystal field splitting energy increases in the order
[Cr(Cl)6]3−<[Cr(NH3)6]3+<[Cr(CN)6]3−
17. Write the coordination number and oxidation state of Platinum in the complex [Pt(en)2Cl2].→ANS) CN= 4, OS= +2
18. What type of isomerism is exhibited by the complex [Co(NH3)5Cl]SO4 ? →ANS) ionization isomerism
19. What type of isomerism is shown by the complex [Co(NH3)5 (SCN)]2+ ? → ANS) Linkage isomerism
20. Why are low spin tetrahedral complexes rarely observed? → ANS) orbital splitting energies are not enough to force pairing.
21. Why a solution of [Ni(H2O)6] 2+ is green while a solution of [Ni(CN)4] 2– is colourless ?
22. What type of isomerism is shown by the complex [Co(en)3]Cl3 ? → ANS) Optical isomerism
23. Define crystal field splitting energy?
24. When a coordination compound 𝐂𝐨𝐂𝐥𝟑. 𝟔𝐍𝐇𝟑 is mixed with 𝐀𝐠𝐍𝐎𝟑, 3 moles of AgCl are precipitated per mole of the
compound. Write (i) Structural formula of the complex (ii) IUPAC name of the complex.
ANS) [Co(NH3)6]Cl3 → Hexaamminecobalt(III) Chloride
25. What type of isomerism is shown by the complex[𝑪𝒓(𝑯𝟐𝑶)𝟔]𝑪𝒍𝟑? → ANS) Solvate isomerism
26. What is the Denticity of a ligand? → ANS) the number of pairs of electrons shared with the metal atom
27. Calculate the overall complex dissociation equilibrium constant for the [Cu(𝑵𝑯𝟑)4] 2+ ion, given that 𝜷𝟒 for this complex is 𝟐.
𝟏×𝟏𝟎𝟏𝟑. → ANS) The overall complex dissociation equilibrium constant is the reciprocal of the overall stability constant, β4.

28. For the complex [𝑭𝒆(𝒆𝒏)𝟐C𝒍𝟐]𝑪𝒍, (en=ethylene diamine), identify (i) The oxidation number of iron, (ii) The hybrid orbits and
the shape of the complex, (iii) The magnetic behavior of the complex. (iv) The number of geometrical isomers, (v) Whether
there is an optical isomer also, and (vi) name of the complex. (At. No. of Fe = 26)