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Coordination Compounds question

2011 · Shift 2 · Q8
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Coordination Compounds question

2011 · Shift 2 · Q8

JEE AdvancedChemistryCoordination CompoundsMCQ+3 / −1
Among the following complexes (K-P), K3[Fe(CN)6]K_3[Fe(CN)_6]K3​[Fe(CN)6​] (K), [Co(NH3)6]Cl3[Co(NH_3)_6]Cl_3[Co(NH3​)6​]Cl3​ (L), Na3[Co(oxalate)3]Na_3[Co(oxalate)_3]Na3​[Co(oxalate)3​] (M), [Ni(H2O)3]Cl2[Ni(H_2O)_3]Cl_2[Ni(H2​O)3​]Cl2​ (N), K2[Pt(CN)4]K_2[Pt(CN)_4]K2​[Pt(CN)4​] (O) and [Zn(H2O)6(NO3)2][Zn(H_2O)_6(NO_3)_2][Zn(H2​O)6​(NO3​)2​] (P) The diamagnetic complexes are
  1. A
    K, L, M, N
  2. B
    K, M, O, P
  3. C
    L, M, O, P
  4. D
    L, M, N, O
View written solutionFree

Correct answer: C

To determine which of the complexes are diamagnetic, we need to find the number of unpaired electrons in the d-orbitals of the central metal ion in each complex. A complex is diamagnetic if it has zero unpaired electrons. This involves determining the oxidation state of the metal, its d-electron configuration, the geometry of the complex, and the effect of the ligands (strong-field or weak-field) on the electron arrangement.

Let's analyze each complex:

1. K: K3[Fe(CN)6]K_3[Fe(CN)_6]K3​[Fe(CN)6​]

  • Central metal ion: Iron (Fe).
  • Oxidation state: The complex ion is [Fe(CN)6]3−[Fe(CN)_6]^{3-}[Fe(CN)6​]3−. Let the oxidation state of Fe be xxx. Cyanide (CN−CN^-CN−) has a charge of -1. So, x+6(−1)=−3x + 6(-1) = -3x+6(−1)=−3, which gives x=+3x = +3x=+3. The ion is Fe3+Fe^{3+}Fe3+.
  • Electron configuration: Fe (Z=26) is [Ar]3d64s2[Ar] 3d^6 4s^2[Ar]3d64s2. So, Fe3+Fe^{3+}Fe3+ is [Ar]3d5[Ar] 3d^5[Ar]3d5.
  • Ligand and Geometry: CN−CN^-CN− is a strong-field ligand. The geometry is octahedral. For a d5d^5d5 ion with a strong-field ligand, the complex is low-spin. The electrons will pair up in the lower energy t2gt_{2g}t2g​ orbitals first.
  • d-orbital filling: The configuration is t2g5eg0t_{2g}^5 e_g^0t2g5​eg0​. The five electrons in the three t2gt_{2g}t2g​ orbitals will be arranged as (↑↓)(↑↓)(↑)(\uparrow\downarrow)(\uparrow\downarrow)(\uparrow)(↑↓)(↑↓)(↑).
  • Conclusion: There is one unpaired electron. The complex is paramagnetic.

2. L: [Co(NH3)6]Cl3[Co(NH_3)_6]Cl_3[Co(NH3​)6​]Cl3​

  • Central metal ion: Cobalt (Co).
  • Oxidation state: The complex ion is [Co(NH3)6]3+[Co(NH_3)_6]^{3+}[Co(NH3​)6​]3+. Ammonia (NH3NH_3NH3​) is a neutral ligand. So, the oxidation state of Co is +3. The ion is Co3+Co^{3+}Co3+.
  • Electron configuration: Co (Z=27) is [Ar]3d74s2[Ar] 3d^7 4s^2[Ar]3d74s2. So, Co3+Co^{3+}Co3+ is [Ar]3d6[Ar] 3d^6[Ar]3d6.
  • Ligand and Geometry: NH3NH_3NH3​ acts as a strong-field ligand with Co3+Co^{3+}Co3+. The geometry is octahedral. The complex is low-spin.
  • d-orbital filling: The configuration is t2g6eg0t_{2g}^6 e_g^0t2g6​eg0​. The six electrons fill the three t2gt_{2g}t2g​ orbitals, pairing up completely: (↑↓)(↑↓)(↑↓)(\uparrow\downarrow)(\uparrow\downarrow)(\uparrow\downarrow)(↑↓)(↑↓)(↑↓).
  • Conclusion: There are zero unpaired electrons. The complex is diamagnetic.

3. M: Na3[Co(oxalate)3]Na_3[Co(oxalate)_3]Na3​[Co(oxalate)3​]

  • Central metal ion: Cobalt (Co).
  • Oxidation state: The complex ion is [Co(C2O4)3]3−[Co(C_2O_4)_3]^{3-}[Co(C2​O4​)3​]3−. Oxalate (C2O42−C_2O_4^{2-}C2​O42−​) has a charge of -2. Let the oxidation state of Co be xxx. So, x+3(−2)=−3x + 3(-2) = -3x+3(−2)=−3, which gives x=+3x = +3x=+3. The ion is Co3+Co^{3+}Co3+.
  • Electron configuration: Co3+Co^{3+}Co3+ is [Ar]3d6[Ar] 3d^6[Ar]3d6.
  • Ligand and Geometry: Oxalate is a bidentate ligand, so the geometry is octahedral. For Co3+Co^{3+}Co3+, most ligands (including oxalate) cause electron pairing, leading to a low-spin complex.
  • d-orbital filling: The configuration is t2g6eg0t_{2g}^6 e_g^0t2g6​eg0​. All six electrons are paired in the t2gt_{2g}t2g​ orbitals.
  • Conclusion: There are zero unpaired electrons. The complex is diamagnetic.

4. N: [Ni(H2O)6]Cl2[Ni(H_2O)_6]Cl_2[Ni(H2​O)6​]Cl2​ (assuming the common hexaaqua complex, as [Ni(H2O)3]Cl2[Ni(H_2O)_3]Cl_2[Ni(H2​O)3​]Cl2​ is an unusual representation for a monomeric species).

  • Central metal ion: Nickel (Ni).
  • Oxidation state: The complex ion is [Ni(H2O)6]2+[Ni(H_2O)_6]^{2+}[Ni(H2​O)6​]2+. Water (H2OH_2OH2​O) is a neutral ligand. So, the oxidation state of Ni is +2. The ion is Ni2+Ni^{2+}Ni2+.
  • Electron configuration: Ni (Z=28) is [Ar]3d84s2[Ar] 3d^8 4s^2[Ar]3d84s2. So, Ni2+Ni^{2+}Ni2+ is [Ar]3d8[Ar] 3d^8[Ar]3d8.
  • Ligand and Geometry: H2OH_2OH2​O is a weak-field ligand. The geometry is octahedral. The complex is high-spin.
  • d-orbital filling: The configuration is t2g6eg2t_{2g}^6 e_g^2t2g6​eg2​. The electrons fill the orbitals as (↑↓)(↑↓)(↑↓)(\uparrow\downarrow)(\uparrow\downarrow)(\uparrow\downarrow)(↑↓)(↑↓)(↑↓) in t2gt_{2g}t2g​ and (↑)(↑)(\uparrow)(\uparrow)(↑)(↑) in ege_geg​.
  • Conclusion: There are two unpaired electrons. The complex is paramagnetic.

5. O: K2[Pt(CN)4]K_2[Pt(CN)_4]K2​[Pt(CN)4​]

  • Central metal ion: Platinum (Pt).
  • Oxidation state: The complex ion is [Pt(CN)4]2−[Pt(CN)_4]^{2-}[Pt(CN)4​]2−. So, x+4(−1)=−2x + 4(-1) = -2x+4(−1)=−2, which gives x=+2x = +2x=+2. The ion is Pt2+Pt^{2+}Pt2+.
  • Electron configuration: Pt (Z=78) is a 5d element. Its configuration is [Xe]4f145d96s1[Xe] 4f^{14} 5d^9 6s^1[Xe]4f145d96s1. So, Pt2+Pt^{2+}Pt2+ is [Xe]4f145d8[Xe] 4f^{14} 5d^8[Xe]4f145d8.
  • Ligand and Geometry: CN−CN^-CN− is a strong-field ligand. For d8d^8d8 ions of 4d and 5d series, square planar geometry is highly favored. This leads to a low-spin configuration.
  • d-orbital filling: In a square planar field, the 8 electrons fill the lower four d-orbitals (dxz,dyz,dz2,dxyd_{xz}, d_{yz}, d_{z^2}, d_{xy}dxz​,dyz​,dz2​,dxy​), leaving the high-energy dx2−y2d_{x^2-y^2}dx2−y2​ orbital empty. All electrons are paired.
  • Conclusion: There are zero unpaired electrons. The complex is diamagnetic.

6. P: [Zn(H2O)6](NO3)2[Zn(H_2O)_6](NO_3)_2[Zn(H2​O)6​](NO3​)2​ (assuming standard notation where nitrate is the counter-ion).

  • Central metal ion: Zinc (Zn).
  • Oxidation state: The complex ion is [Zn(H2O)6]2+[Zn(H_2O)_6]^{2+}[Zn(H2​O)6​]2+. So, the oxidation state of Zn is +2. The ion is Zn2+Zn^{2+}Zn2+.
  • Electron configuration: Zn (Z=30) is [Ar]3d104s2[Ar] 3d^{10} 4s^2[Ar]3d104s2. So, Zn2+Zn^{2+}Zn2+ is [Ar]3d10[Ar] 3d^{10}[Ar]3d10.
  • Ligand and Geometry: The d-subshell is completely filled.
  • d-orbital filling: A d10d^{10}d10 configuration means all d-orbitals are filled with paired electrons, regardless of the ligand field strength or geometry.
  • Conclusion: There are zero unpaired electrons. The complex is diamagnetic.

Summary: The diamagnetic complexes are L, M, O, and P. This corresponds to option C.

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