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Coordination Compounds question

2021 · Shift 2 · Q5
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  5. /2021 · Shift 2 · Q5

Coordination Compounds question

2021 · Shift 2 · Q5

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)
  1. A
    [FeCl4]−[FeCl_4]^-[FeCl4​]− and [Fe(CO)4]2−[Fe(CO)_4]^{2-}[Fe(CO)4​]2−
  2. B
    [Co(CO)4]−[Co(CO)_4]^-[Co(CO)4​]− and [CoCl4]2−[CoCl_4]^{2-}[CoCl4​]2−
  3. C
    [Ni(CO)4{}_44​] and [Ni(CN)4{}_44​]2−{}^{2-}2−
  4. D
    [Cu(py)4{}_44​]+{}^++ and [Cu(CN)4{}_44​]3−{}^{3-}3−
View written solutionFree

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 (sp3sp^3sp3 hybridization) or square planar (dsp2dsp^2dsp2 hybridization).

General Rules:

  1. Determine the oxidation state of the central metal ion.
  2. Write down the electronic configuration of the central metal ion.
  3. For coordination number 4:
    • If the central metal ion has a d10d^{10}d10 electronic configuration, the hybridization will be sp3sp^3sp3 and the geometry will be tetrahedral, as there are no vacant d-orbitals for dsp2dsp^2dsp2 hybridization.
    • If the central metal ion has a d8d^8d8 configuration with a strong field ligand (like CN−CN^-CN−, COCOCO), electron pairing occurs, making one d-orbital vacant, leading to dsp2dsp^2dsp2 hybridization and square planar geometry.
    • If the ligands are weak field (like halides Cl−Cl^-Cl−, Br−Br^-Br−), they generally do not cause pairing. If no inner d-orbital is available, the hybridization will be sp3sp^3sp3, leading to tetrahedral geometry.

Let's analyze each option:

A: [FeCl4]−[FeCl_4]^-[FeCl4​]− and [Fe(CO)4]2−[Fe(CO)_4]^{2-}[Fe(CO)4​]2−

  1. [FeCl4]−[FeCl_4]^-[FeCl4​]−:

    • Oxidation state of Fe: Let it be xxx. x+4(−1)=−1⇒x=+3x + 4(-1) = -1 \Rightarrow x = +3x+4(−1)=−1⇒x=+3.
    • Fe (Z=26) has the configuration [Ar]3d64s2[Ar] 3d^6 4s^2[Ar]3d64s2.
    • Fe3+Fe^{3+}Fe3+ has the configuration [Ar]3d5[Ar] 3d^5[Ar]3d5.
    • Cl−Cl^-Cl− 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 sp3sp^3sp3, which corresponds to a tetrahedral geometry.
  2. [Fe(CO)4]2−[Fe(CO)_4]^{2-}[Fe(CO)4​]2−:

    • Oxidation state of Fe: Let it be xxx. x+4(0)=−2⇒x=−2x + 4(0) = -2 \Rightarrow x = -2x+4(0)=−2⇒x=−2.
    • Fe (Z=26) has the configuration [Ar]3d64s2[Ar] 3d^6 4s^2[Ar]3d64s2.
    • Fe−2Fe^{-2}Fe−2 has the electronic configuration [Ar]3d84s2[Ar] 3d^8 4s^2[Ar]3d84s2.
    • COCOCO is a strong field ligand, which causes the 4s electrons to shift to the 3d orbitals.
    • The resulting configuration of Fe is [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
    • Since the 3d orbitals are completely filled, the hybridization must be sp3sp^3sp3.
    • The geometry is tetrahedral.

Since both complexes in pair A are tetrahedral, option A is correct.

B: [Co(CO)4]−[Co(CO)_4]^-[Co(CO)4​]− and [CoCl4]2−[CoCl_4]^{2-}[CoCl4​]2−

  1. [Co(CO)4]−[Co(CO)_4]^-[Co(CO)4​]−:

    • Oxidation state of Co: Let it be xxx. x+4(0)=−1⇒x=−1x + 4(0) = -1 \Rightarrow x = -1x+4(0)=−1⇒x=−1.
    • Co (Z=27) has the configuration [Ar]3d74s2[Ar] 3d^7 4s^2[Ar]3d74s2.
    • Co−1Co^{-1}Co−1 has the configuration [Ar]3d84s2[Ar] 3d^8 4s^2[Ar]3d84s2.
    • CO is a strong field ligand, pushing the 4s electrons into the 3d orbitals.
    • The resulting configuration of Co is [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
    • The 3d orbitals are full, so hybridization is sp3sp^3sp3.
    • The geometry is tetrahedral.
  2. [CoCl4]2−[CoCl_4]^{2-}[CoCl4​]2−:

    • Oxidation state of Co: Let it be xxx. x+4(−1)=−2⇒x=+2x + 4(-1) = -2 \Rightarrow x = +2x+4(−1)=−2⇒x=+2.
    • Co (Z=27) has the configuration [Ar]3d74s2[Ar] 3d^7 4s^2[Ar]3d74s2.
    • Co2+Co^{2+}Co2+ has the configuration [Ar]3d7[Ar] 3d^7[Ar]3d7.
    • Cl−Cl^-Cl− is a weak field ligand. It does not cause electron pairing.
    • Hybridization involves the outer 4s and 4p orbitals, leading to sp3sp^3sp3 hybridization.
    • The geometry is tetrahedral.

Since both complexes in pair B are tetrahedral, option B is correct.

C: [Ni(CO)4{}_44​] and [Ni(CN)4{}_44​]2−{}^{2-}2−

  1. [Ni(CO)4{}_44​]:

    • Oxidation state of Ni is 0.
    • Ni (Z=28) has the configuration [Ar]3d84s2[Ar] 3d^8 4s^2[Ar]3d84s2.
    • CO is a strong field ligand, so the 4s electrons are pushed into the 3d orbitals.
    • The resulting configuration of Ni is [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
    • With a filled 3d subshell, the hybridization is sp3sp^3sp3.
    • The geometry is tetrahedral.
  2. [Ni(CN)4{}_44​]2−{}^{2-}2−:

    • Oxidation state of Ni: Let it be xxx. x+4(−1)=−2⇒x=+2x + 4(-1) = -2 \Rightarrow x = +2x+4(−1)=−2⇒x=+2.
    • Ni (Z=28) has the configuration [Ar]3d84s2[Ar] 3d^8 4s^2[Ar]3d84s2.
    • Ni2+Ni^{2+}Ni2+ has the configuration [Ar]3d8[Ar] 3d^8[Ar]3d8.
    • CN−CN^-CN− is a strong field ligand. It forces the pairing of the two unpaired 3d electrons.
    • This leaves one 3d orbital empty (dx2−y2d_{x^2-y^2}dx2−y2​).
    • The hybridization is dsp2dsp^2dsp2 (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)4{}_44​]+{}^++ and [Cu(CN)4{}_44​]3−{}^{3-}3−

  1. [Cu(py)4{}_44​]+{}^++:

    • Pyridine (py) is a neutral ligand.
    • Oxidation state of Cu is +1.
    • Cu (Z=29) has the configuration [Ar]3d104s1[Ar] 3d^{10} 4s^1[Ar]3d104s1.
    • Cu+Cu^{+}Cu+ has the configuration [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
    • The 3d orbitals are completely filled. Hybridization must be sp3sp^3sp3.
    • The geometry is tetrahedral.
  2. [Cu(CN)4{}_44​]3−{}^{3-}3−:

    • Oxidation state of Cu: Let it be xxx. x+4(−1)=−3⇒x=+1x + 4(-1) = -3 \Rightarrow x = +1x+4(−1)=−3⇒x=+1.
    • Cu+Cu^{+}Cu+ has the configuration [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
    • The 3d orbitals are completely filled. Hybridization must be sp3sp^3sp3.
    • The geometry is tetrahedral.

Since both complexes in pair D are tetrahedral, option D is correct.

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