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Coordination Compounds - Notes

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Coordination Compounds - Notes

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CHEMISTRY CLASS XII

Chapter 9 – Coordination Compounds


Isomerism in Coordination Compounds
Isomers :
• Compounds with same chemical formula but a different structural formulae or spatial arrangement are
called isomers
• they differ in one or more physical or chemical properties

(A) Structural isomerism

(i) Linkage isomerism


• Arises in a coordination compound containing ambidentate ligand.
• Example : [Co(NH3)5(NO2)]Cl2
(ii) Coordination isomerism
• Arises when both the anionic and cationic part of the compound are complexes
• interchange of ligands between cationic and anionic entities occur
• Example : [Co(NH3)6][Cr(CN)6]
(iii) Ionisation isomerism
• They give different ions in solution even when they have same molecular formula
• Arises when the counter ion in a complex salt is itself a potential ligand
• Example : [Co(NH3)5SO4]Br
(iv) Solvate isomerism
• Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion or
merely present as free solvent molecules in the crystal lattice.
• Example : [Cr(H2O)6]Cl3

(B) Stereoisomerism
(i) Geometrical isomerism : arises in heteroleptic complexes of coordination numbers 4(square plannar
complexes) & 6(octahedral complexes)
TYPES : Cis-trans & Fac-mer

MX2L2 /[Pt(NH3)2Cl2]

MAXL2 / [Pt(NH3)2BrCl]

MABXL / [Pt(NH3)PyBrCl]

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CHEMISTRY CLASS XII
Chapter 9 – Coordination Compounds

MX2L4 / [Cr(NH3)4Cl2]+

MX2(L-L)2 / [CoCl2(en)2]+

MA3B3 : [Co(NH3)3(NO2)3] Fac-mer isomerism

(ii) Optical Isomerism

• Optical isomers are mirror images that cannot be superimposed on one another (chiral –optically active)
• Common in octahedral complexes involving didentate ligands
• Example : cis-[CoCl2(en)2]+ [Co(en)3]3+ [Co(ox)3]3- [Co(en)(NH3)2Cl2]+

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CHEMISTRY CLASS XII
Chapter 9 – Coordination Compounds

Bonding in Coordination Compounds


Theories : Werner’s theory , VBT , CFT , LFT (Ligand Field Theory) , MOT(Molecular Orbital Theory)

Limitations of Werner’s theory: It can not explain


➢ Why only certain elements form complexes
➢ Directional properties of bonds in complexes
➢ Magnetic and optical properties of complexes

Valence Bond Theory


• Hybridization: the metal atom or ion undergo hybridization under the influence of ligands
o It can use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation
o A set of equivalent orbitals are produced
o The hybridized orbitals will have definite geometry such as octahedral, tetrahedral, square planar
etc.
• Overlapping : These hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron
pairs for bonding

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CHEMISTRY CLASS XII
Chapter 9 – Coordination Compounds
Inner orbital complex :
➢ Uses inner d-orbitals for bonding
➢ They are low spin or spin paired complexes
Outer orbital complex
➢ Uses outer d-orbitals for bonding
➢ They are high spin or spin free complexes

[Co(NH3)6]3+ [CoF6]3- [Ni(CO)4] [NiCl4]2- [Ni(CN)4]2-

Explain the following using VBT:


1. [Mn(CN)6]3- has magnetic moment of two unpaired electrons while [MnCl6]3- paramagnetic moment of four
unpaired electrons.
2. [Fe(CN)6]3- has magnetic moment of a single unpaired electron while [FeF6]3– has a paramagnetic moment
of five unpaired electrons.
3. [CoF6]3– is paramagnetic with four unpaired electrons while [Co(C2O4)3]3– is diamagnetic
Limitations :

(i) It involves a number of assumptions.


(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination compounds.
(iv) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordination
compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar structures of 4-coordinate
complexes.
(vi) It does not distinguish between weak and strong ligands.

Crystal Field Theory


➢ Ligands are treated as point charges (anions) or dipoles(neutral molecules)
➢ Metal-ligand bond is considered to be purely ionic (electrostatic force of attraction)
➢ The five d orbitals in an isolated gaseous metal atom/ion have same energy, i.e., they are degenerate.
➢ Crystal Field Splitting : Under the influence of ligands the energy of d-orbitals are lifted . Finally, the five
degenerate d-orbitals of the metal ion split into different sets of orbitals having different energies in the
presence of electrical field of the ligands.
➢ Nature of splitting of d-orbitals depends on the co-ordination number

Orientations of d-orbitals
• dxy , dyz , dxz orbitals → in between the principal axes
• dx2-y2 , dz2 orbitals → along the axes

(a) Crystal field splitting in octahedral coordination entities


Ligands approaches the central metal ion along the axes

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CHEMISTRY CLASS XII
Chapter 9 – Coordination Compounds

➢ The energy of the two eg orbitals will increase by (3/5) Δ O and that of the three t2g orbitals will decrease by
(2/5)ΔO

(b) Crystal field splitting in tetrahedral coordination entities


Ligands approaches the central metal ion in between the axes the axes

➢ Tetrahedral field splitting is smaller as compared to the octahedral field splitting.


➢ For the same metal, the same ligands and metal-ligand distances, it can be shown that Δt = (4/9) Δ O
➢ Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, therefore, low
spin configurations are rarely observed.

Note:

✓ Crystal Field Splitting Energy (Δo/Δt) – Energy gap between t2g & eg orbitals
✓ Pairing Energy (P) – Energy required to pair the electrons in an orbital
✓ Spectrochemical Series – Arrangement of ligands in the order of their field strength
I – > Br – > SCN – >Cl – > S2 – > F – > OH – > C2O42 – > H2O > NCS – > edta 4– > NH3 > en > CN – > CO
✓ Weak field ligands form high spin complexes because Δo < P
✓ Strong field ligands form low spin complexes because Δo < P

What are the important factors which governs the magnitude of crystal field splitting (Δ)?
• Nature & oxidation state of the metal ion
• Nature of ligands
• Geometry of the complex

Colour in Coordination Compounds


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CHEMISTRY CLASS XII
Chapter 9 – Coordination Compounds
• It is due to d-d transition

• The colour of the complex is complementary to that which is absorbed.

QUESTIONS:
1. Explain the violet colour of [Ti(H2O)6]3+ in terms of CFT.
2. Even though [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2 are octahedral complexes their colours are different (violet &
blue-green) . Why?
3. removal of water from [Ti(H2O)6]Cl3 on heating renders it colourless.Why ?
4. anhydrous CuSO4 is white, but CuSO4.5H2O is blue in colour .Why?
5. what are the limitations of CFT ?
6. Treated ligands only as point charges
7. Can not explain why the field strength neutral moleculs are more than the anions
8. Tatally avoided the covalent character of metal-ligand bond
9. ame the following coordination compounds and draw their structures.
(i) [CoCl2 (en)2] Cl (ii) [Pt(NH3)2Cl(NO2)] [At. No. of Co = 27, Pt = 78)
10. Compare the following complexes with respect to their molecular shape and magnetic behaviour.
(i) [Cr(NH3)6]3+ (ii) [Fe(CN)6] 4– (iii) [NiCl4] 2 – (Atomic number of Cr = 24, Fe = 26 and Ni = 28)
11. Describe the state of hybridization, the shape and the magnetic behaviour of the following complexes.
(i) [Cr(H2O)2(C2O4)2] – (ii) [Co(NH3)2(en)2]3+ (iii) [Pt(NH3)Cl (NO2)] (iv) [Co(NH3)4Cl2] Cl
2–
(v) Ni(CO)4 (vi) [Ni(CNB)4] (vii) K4[Mn(CN)6]. (viii) [Co(en)2 Cl (ONO)]+.
12. Write the name, stereochemistry and magnetic behaviour of the following:
(i) K4[Mn(CN)6] (ii) [Co(NH3)5Cl] Cl2 (iii) K2[Ni(CN)4]
13. Write the structures and names of all the stereo isomers of the following compounds.
(i) [Co (en)3]Cl2 (ii) [Pt(NH3)2Cl2] (iii) [Fe(NH3)4Cl2] Cl
14. Write the name and draw the structures of each of the following complex compounds :
(i) [Co(NH3)4(H2O)2]Cl3 (ii) [Pt(NH3)4] [NiCl4]
15. Explain the following cases giving appropriate reasons.
(i) Nickel does not form low spin octahedral complexes
(ii) The -complexes are known for the transition metals only
(iii) Co2+ is easily oxidized to Co3+ in the presence of a strong ligand
16. Explain as to how the two complexes of nickel, [Ni(CN) 4]2– and [Ni (CO)4] have different structure but do not
differ in their magnetic behaviour (Ni = 28)
17. What is the basis of formation of the spectro-chemical series ?
18. Draw the structure of Cis – [Co(NH3)4Cl2]+ and write the hybridization state of Co in the given complex
entity.

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