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Ni Complexes: Hybridization & Magnetism

Among the complexes Ni(CO)4, [Ni(CN)4]2-, and NiCl42-, Ni(CO)4 and [Ni(CN)4]2- are diamagnetic as their d-electrons are paired up due to strong ligand fields. NiCl42- is paramagnetic as its weak chloride ligands do not cause pairing of d-electrons, leaving unpaired electrons. Therefore, the correct option is that Ni(CO)4 and [Ni(CN)4]2- are diamagnetic, while NiCl42- is paramagnetic.

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Isaiah Makurunje
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55 views3 pages

Ni Complexes: Hybridization & Magnetism

Among the complexes Ni(CO)4, [Ni(CN)4]2-, and NiCl42-, Ni(CO)4 and [Ni(CN)4]2- are diamagnetic as their d-electrons are paired up due to strong ligand fields. NiCl42- is paramagnetic as its weak chloride ligands do not cause pairing of d-electrons, leaving unpaired electrons. Therefore, the correct option is that Ni(CO)4 and [Ni(CN)4]2- are diamagnetic, while NiCl42- is paramagnetic.

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Isaiah Makurunje
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1) Amongst Ni(CO)4, [Ni(CN)4]2- 

and NiCl42-:
(IIT JEE 1991)
a) Ni(CO)4 and NiCl42- are diamagnetic; and [Ni(CN)4] 2- is paramagnetic.
b) [Ni(CN)4]2- and NiCl42- are diamagnetic; and Ni(CO)4 is paramagnetic.
c) Ni(CO)4 and [Ni(CN)4]2- are diamagnetic; and NiCl42- is paramagnetic.
d) Ni(CO)4 is diamagnetic; [Ni(CN)4]2- and NiCl42- are paramagnetic.
Logic & Solution:
Ni(CO)4 = Ni + 4CO
* The valence shell electronic configuration of ground state Ni atom is
3d8 4s2. 
* All of these 10 electrons are pushed into 3d orbitals and get paired up
when strong field CO ligands approach Ni atom. The empty 4s and three 4p
orbitals undergo sp3 hybridization and form bonds with CO ligands to give
Ni(CO)4. Thus Ni(CO)4 is diamagnetic.

KEY POINTS:
Ni(CO)4 Hybridization:sp3
Ni(CO)4 Shape & Structure (geometry): Tetrahedral
Ni(CO)4 Magnetic nature: Diamagnetic (low spin)
[Ni(CN)4]2- = Ni2+ + 4CN-
* In [Ni(CN)4]2-, there is Ni2+ ion for which the electronic configuration in
the valence shell is 3d8 4s0.
* In presence of strong field CN- ions, all the electrons are paired up. The
empty 4d, 3s and two 4p orbitals undergo dsp 2 hybridization to make bonds
with CN- ligands in square planar geometry. Thus [Ni(CN)4]2- is diamagnetic. 

KEY POINTS:
[Ni(CN)4]2- Hybridization:dsp2
[Ni(CN)4]2- Shape: Square planar
[Ni(CN)4]2- Magnetic nature: Diamagnetic (low spin)
NiCl42- = Ni2+ + 4Cl-
* Again in NiCl42-, there is Ni2+ ion, However, in presence of weak field
Cl- ligands, NO pairing of d-electrons occurs. Therefore, Ni2+ undergoes
sp3 hybridization to make bonds with Cl - ligands in tetrahedral geometry. As
there are unpaired electrons in the d-orbitals, NiCl 42- is paramagnetic and is
referred to as a high spin complex. 
 

KEY POINTS:
[NiCl4]2- Hybridization:sp3
[NiCl4]2- Shape & Structure: Tetrahedral
[NiCl4]2- Magnetic nature: Paramagnetic (low spin)

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