JEE AdvancedChemistryCoordination CompoundsMultiple correct+4 / −2
The pair(s) of complexes wherein both exhibit tetrahedral geometry is(are) (Note : py = pyridine) Given : Atomic numbers of Fe, Co, Ni and Cu are 26, 27, 28 and 29, respectively)
- Aand
- Band
- C[Ni(CO)] and [Ni(CN)]
- D[Cu(py)] and [Cu(CN)]
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Correct answer: A, B, D
To determine the geometry of the coordination complexes, we need to find the hybridization of the central metal atom. For a coordination number of 4, the geometry can be either tetrahedral ( hybridization) or square planar ( hybridization).
General Rules:
- Determine the oxidation state of the central metal ion.
- Write down the electronic configuration of the central metal ion.
- For coordination number 4:
- If the central metal ion has a electronic configuration, the hybridization will be and the geometry will be tetrahedral, as there are no vacant d-orbitals for hybridization.
- If the central metal ion has a configuration with a strong field ligand (like , ), electron pairing occurs, making one d-orbital vacant, leading to hybridization and square planar geometry.
- If the ligands are weak field (like halides , ), they generally do not cause pairing. If no inner d-orbital is available, the hybridization will be , leading to tetrahedral geometry.
Let's analyze each option:
A: and
-
:
- Oxidation state of Fe: Let it be . .
- Fe (Z=26) has the configuration .
- has the configuration .
- is a weak field ligand. It does not cause electron pairing.
- For coordination number 4, the vacant orbitals available for hybridization are one 4s and three 4p orbitals.
- Hybridization is , which corresponds to a tetrahedral geometry.
-
:
- Oxidation state of Fe: Let it be . .
- Fe (Z=26) has the configuration .
- has the electronic configuration .
- is a strong field ligand, which causes the 4s electrons to shift to the 3d orbitals.
- The resulting configuration of Fe is .
- Since the 3d orbitals are completely filled, the hybridization must be .
- The geometry is tetrahedral.
Since both complexes in pair A are tetrahedral, option A is correct.
B: and
-
:
- Oxidation state of Co: Let it be . .
- Co (Z=27) has the configuration .
- has the configuration .
- CO is a strong field ligand, pushing the 4s electrons into the 3d orbitals.
- The resulting configuration of Co is .
- The 3d orbitals are full, so hybridization is .
- The geometry is tetrahedral.
-
:
- Oxidation state of Co: Let it be . .
- Co (Z=27) has the configuration .
- has the configuration .
- is a weak field ligand. It does not cause electron pairing.
- Hybridization involves the outer 4s and 4p orbitals, leading to hybridization.
- The geometry is tetrahedral.
Since both complexes in pair B are tetrahedral, option B is correct.
C: [Ni(CO)] and [Ni(CN)]
-
[Ni(CO)]:
- Oxidation state of Ni is 0.
- Ni (Z=28) has the configuration .
- CO is a strong field ligand, so the 4s electrons are pushed into the 3d orbitals.
- The resulting configuration of Ni is .
- With a filled 3d subshell, the hybridization is .
- The geometry is tetrahedral.
-
[Ni(CN)]:
- Oxidation state of Ni: Let it be . .
- Ni (Z=28) has the configuration .
- has the configuration .
- is a strong field ligand. It forces the pairing of the two unpaired 3d electrons.
- This leaves one 3d orbital empty ().
- The hybridization is (using one 3d, one 4s, and two 4p orbitals).
- The geometry is square planar.
Since one complex is tetrahedral and the other is square planar, option C is incorrect.
D: [Cu(py)] and [Cu(CN)]
-
[Cu(py)]:
- Pyridine (py) is a neutral ligand.
- Oxidation state of Cu is +1.
- Cu (Z=29) has the configuration .
- has the configuration .
- The 3d orbitals are completely filled. Hybridization must be .
- The geometry is tetrahedral.
-
[Cu(CN)]:
- Oxidation state of Cu: Let it be . .
- has the configuration .
- The 3d orbitals are completely filled. Hybridization must be .
- The geometry is tetrahedral.
Since both complexes in pair D are tetrahedral, option D is correct.
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