15. Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory:
(i) [Fe(CN)6]4–
(ii) [FeF6]3–
(iii) [Co(C2O4)3]3–
(iv) [CoF6]3-
Answer:
(i) Fe(CN)6]4−
In this coordination complex, the oxidation state of Fe is +3.
Fe 2+ : Electronic configuration is 3d6
Orbitals of Fe2+ ion :

Since CN− is a strong field ligand, it causes the unpaired 3d electrons to pair up:

As there are six ligands around the central metal ion, the most practical hybridization is d2sp3, d2sp3 hybridized orbitals of Fe2+ are:

6 electron pairs from CN − ions take the place of the six hybrid d2sp3 orbitals.
Then,

Thus, the geometry of the complex is octahedral and it is a diamagnetic complex (since all the electrons are paired).
(ii) [FeF6] 3−
In this coordinate entity, the oxidation state of iron is +3.
Orbitals of Fe +3 ion:

There are 6 F− ions. Hence, it will go through d2sp3 or sp3d2 hybridization.
Since F− is a weak field ligand, it does not cause the pairing of the electrons in the 3d orbital. Thus, the most practical hybridization is sp3d2. sp3d 2 hybridized orbitals of Fe are :

Thus, the geometry of this coordinate entity is octahedral.
(iii) [Co( C2O4)3]3−
In this complex, the oxidation state of cobalt is +3.
Orbitals of Co 3+ ion :

Oxalate is a weak field ligand. Thus, it will not cause the pairing of the 3d orbital electrons.
As there are 6 ligands, hybridization has to be either sp3d 2 or d 2sp3 hybridization.
sp3d2 hybridization of Co 3+ :

The 6 electron pairs from the 3 oxalate ions (oxalate anion is a bidentate ligand) occupy these sp3d 2 orbitals :

Thus, the complex shows octahedral geometry.
(iv) [CoF6]3−
In this complex, Cobalt has an oxidation state of +3.
Orbitals of Co3+ ion:

As fluoride ion is a weak field ligand it will not cause the 3d electrons to pair. Hence, the Co3+ ion will go through sp3d2 hybridization.
sp3d2 hybridized orbitals of Co3+ ion are :

Thus, the complex has a geometric configuration of an octahedral and it is paramagnetic.
16. Draw figure to show the splitting of d orbitals in an octahedral crystal field.
Answer:

17. What is the spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
Answer:
A series of common ligands in ascending order of their crystal-field splitting energy (CFSE) is termed as the Spectrochemical series.
Strong field ligands have larger values of CFSE. Whereas, weak field ligands have smaller values of CFSE.
18. What is crystal field splitting energy? How does the magnitude of ∆o decide the actual configuration of d orbitals in a coordination entity?
Answer:
Crystal-field splitting energy is the difference in the energy between the two levels ( i.e., t2g and eg ) that have split from a degenerated d orbital because of the presence of a ligand. It is symbolized as ∆o.
Once the orbitals split up, electrons start filling the vacant spaces. An electron each goes into the three t2g orbitals, the fourth electron, however, can enter either of the two orbitals:
(1) It can go to the eg orbital ( producing t2g3eg 1 like electronic configuration), or
(2) it can go to the t2g orbitals ( producing t2g4eg 0 like electronic configuration).
This filling of the fourth electron is based on the energy level of ∆o. If a ligand has an ∆o value smaller than the pairing energy, then the fourth electron enters the eg orbital. However, if the value of ∆o is greater than the value of pairing energy, the electron enters t2gorbital.
19. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2– is diamagnetic. Explain why.
Answer:
In [ Ni ( CN)4 ] 2−, Ni has an oxidation state of +2. Thus, it has d 8configuration.
Ni 2+ :

CN − being a strong field ligand causes the electrons in 3d orbitals to pair. This causes, Ni 2+ to undergo dsp2 hybridization.

Since all the electrons are paired, it is diamagnetic in nature.
Cr has an oxidation state of +3. Thus, it has a d 3 configuration. As NH3 is not a strong field ligand it does not cause the electrons in the 3d orbital to pair.
Cr3+ :

It undergoes d2sp3 hybridization and the 3d orbital electrons remain unpaired. Thus, [Ni(CN)4]2− is paramagnetic in nature.
20. A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2– is colourless. Explain
Answer:
[ Ni ( H2O)6 ] 2+ consists of Ni+2 ion with 3d8 electronic configuration. In this configuration, there are two unpaired electrons which cannot pair up because H2O is a weak ligand. Thus, the d – d transition absorbs the incoming light and it emits a green light. Thereby, giving a green colour to the solution.
[Ni ( CN)4]2- consists of Ni+2 ion with 3d8 electronic configuration. But, CN – is present here, which is a strong ligand and in its presence, the unpaired electrons pair up. Thus, there is no d –d transition so no colour.