Match List-I with List-II.
Choose the correct answer from the options given below:
Valence Bond Theory
A.(A)-(III), (B)-(II), (C)-(I), (D)-(IV)
B.(A)-(III), (B)-(I), (C)-(II), (D)-(IV)
C.(A)-(IV), (B)-(I), (C)-(II), (D)-(III)
D.(A)-(IV), (B)-(II), (C)-(I), (D)-(III)
Solution & Explanation
Related Formula
Valence Bond Theory utilizes orbital hybridization configurations (sp³$sp^3$, d²sp³$d^2sp^3$, sp³d²$sp^3d^2$) along with ligand field strengths to predict net magnetic parameters.
Core Logic
Valence Bond Theory
Let us analyze each coordination system:
(A) [MnBr₄]²⁻$[\mathrm{MnBr}_4]^{2-}$: Mn²⁺ (3d⁵)$\mathrm{Mn}^{2+} \ (3d^5)$, weak field Br^- arrow$\mathrm{Br}^- \rightarrow$ no pairing.
Thus, the correct matching is: (A)-(IV), (B)-(II), (C)-(I), (D)-(III)
Pattern Recognition
Strong field neutral carbonyl ligands like CO$\mathrm{CO}$ trigger an absolute shift of s$s$-valence pairs into the inner d$d$-shell, resulting in a fully filled d¹⁰$d^{10}$ configuration and diamagnetic behavior.
Correct Option:(D)
More Coordination Compounds Previous-Year Questions — Page 10
Q33jee_main_2025_24_jan_eveningQualitative Analysis of Cations
Find the compound 'A' from the following reaction sequences.
A aqua-regia B (1) KNO2 | NH4OH, (2) AcOH yellow ppt$$\mathrm{A} \xrightarrow{\text{aqua-regia}} \mathrm{B} \xrightarrow{\text{(1) } \mathrm{KNO}{2} | \mathrm{NH}{4}\mathrm{OH}, \text{ (2) } \mathrm{AcOH}} \text{yellow ppt}$$
A. \text{ZnS}
B. \text{CoS}
C. \text{MnS}
D. \text{NiS}
Solution
Core Logic
This pathway corresponds to the standard confirmatory test for cobalt (Co²⁺$\mathrm{Co}^{2+}$) ions in qualitative inorganic analysis:
CoS$\mathrm{CoS}$ dissolves in aqua regia to yield cobalt chloride (CoCl₂$\mathrm{CoCl}_2$):
CoS + aqua regia arrow CoCl₂$$\mathrm{CoS} + \text{aqua regia} \rightarrow \mathrm{CoCl}_{2}$$
Treating this solution with potassium nitrite (KNO₂$\mathrm{KNO}_{2}$) in the presence of acetic acid (AcOH$\mathrm{AcOH}$) oxidizes Co²⁺$\mathrm{Co}^{2+}$ to Co³⁺$\mathrm{Co}^{3+}$, precipitating potassium cobaltinitrite as a characteristic yellow solid:
A yellow precipitate formed specifically upon adding KNO₂$\mathrm{KNO}_2$ and acetic acid is a definitive signature of potassium cobaltinitrite, K₃[Co(NO₂)₆]$\mathrm{K}_3[\mathrm{Co}(\mathrm{NO}_2)_6]$. This confirms the starting sulfide was CoS$\mathrm{CoS}$.
Chapter Mix
Class 12 Chemistry: Coordination Compounds
Class 11 Chemistry: Qualitative Analysis
Q37jee_main_2025_24_jan_eveningSpectrochemical Series and Colour
When Ethane-1, 2-diamine is added progressively to an aqueous solution of Nickel (II) chloride, the sequence of colour change observed will be:
A. \text{Pale Blue } \rightarrow \text{ Blue } \rightarrow \text{ Green } \rightarrow \text{ Violet}
B. \text{Pale Blue } \rightarrow \text{ Blue } \rightarrow \text{ Violet } \rightarrow \text{ Green}
C. \text{Green } \rightarrow \text{ Pale Blue } \rightarrow \text{ Blue } \rightarrow \text{ Violet}
D. \text{Violet } \rightarrow \text{ Blue } \rightarrow \text{ Pale Blue } \rightarrow \text{ Green}
Solution
Core Logic
An aqueous nickel (II) chloride solution contains the green hexaquarickel(II) complex, [Ni(H₂O)₆]²⁺$[\mathrm{Ni}(\mathrm{H}_{2}\mathrm{O})_{6}]^{2+}$. Ethane-1,2-diamine ('en') is a bidentate ligand that binds more strongly than water, shifting the crystal field splitting parameter (Δₒ$\Delta_o$) to higher energies as it replaces water molecules:
This progressive ligand replacement shifts the absorption spectrum, changing the solution's visible color from Green arrow$\rightarrow$ Pale Blue arrow$\rightarrow$ Blue arrow$\rightarrow$ Violet.
Pattern Recognition
Replacing weak-field ligands (like H₂O$\mathrm{H}_2\mathrm{O}$) with stronger bidentate chelating ligands (like 'en') increases crystal field splitting. For Ni²⁺$\mathrm{Ni}^{2+}$, this ligand substitution always follows the specific chromatic progression: Green arrow$\rightarrow$ Pale Blue arrow$\rightarrow$ Blue arrow$\rightarrow$ Violet.
Chapter Mix
Class 12 Chemistry: Coordination Compounds
Q38jee_main_2025_24_jan_eveningCrystal Field Theory
The conditions and consequence that favours the t2g³ eg¹$t_{2g}^{3} e_{g}^{1}$ configuration in a metal complex are:
A. \text{weak field ligand, high spin complex}
B. \text{strong field ligand, high spin complex}
C. \text{strong field ligand, low spin complex}
D. \text{weak field ligand, low spin complex}
Solution
Core Logic
Consider an octahedral coordination environment for a d⁴$d^4$ transition metal ion configuration:
Weak Field Ligand (WFL):
The crystal field splitting energy is smaller than the pairing energy (Δₒ < P$\Delta_o < P$). Consequently, electrons prefer to occupy the higher-energy eg$e_g$ orbitals rather than pair up in the lower-energy t2g$t_{2g}$ orbitals. This leads to a high spin complex with the configuration:
t2g³ eg¹$$t_{2g}^{3} e_{g}^{1}$$
Strong Field Ligand (SFL):
The splitting energy is larger than the pairing energy (Δₒ > P$\Delta_o > P$). Electrons pair up in the t2g$t_{2g}$ orbitals before occupying the eg$e_g$ subshell, resulting in a low spin complex with the configuration:
t2g⁴ eg⁰$$t_{2g}^{4} e_{g}^{0}$$
Pattern Recognition
An electron occupying an eg$e_g$ orbital before the t2g$t_{2g}$ orbitals are fully paired requires a weak-field ligand. This configuration maximizes the number of unpaired electrons, which is the defining characteristic of a high-spin complex.
Chapter Mix
Class 12 Chemistry: Coordination Compounds
Q28jee_main_2025_24_jan_morningWerner's Theory of Coordination Compounds
One mole of the octahedral complex compound Co(NH₃)₅Cl₃$Co(NH_{3})_{5}Cl_{3}$ gives 3 moles of ions on dissolution in water. One mole of the same complex reacts with excess of AgNO₃$AgNO_{3}$ solution to yield two moles of AgCl(s)$AgCl_{(s)}$. The structure of the complex is:
Moles of AgCl precipitated = Moles of ionizable Cl⁻ ions outside the coordination sphere$$\text{Moles of } AgCl \text{ precipitated} = \text{Moles of ionizable } Cl^{-} \text{ ions outside the coordination sphere}$$
Core Logic
Since 1 mole of the complex yields 2 moles of AgCl(s)$AgCl_{(s)}$, there must be exactly 2 chloride ions outside the coordination sphere to undergo precipitation:
Coordination Number 6 corresponds to either d²sp³$d^2sp^3$ or sp³d²$sp^3d^2$ configuration templates.
Coordination Number 4 corresponds to either sp³$sp^3$ or dsp²$dsp^2$ configuration templates.
Core Logic
Analyzing metal orbital dynamics under varying ligand fields:
(A) [CoF₆]³⁻$[CoF_6]^{3-}$: Co³⁺$Co^{3+}$ (3d⁶$3d^6$) with a weak field ligand (F^-$F^-$) arrow$\rightarrow$ no pairing occurs arrow$\rightarrow$ utilizes outer orbitals arrow$\rightarrow$sp³d²$sp^3d^2$.
(B) [NiCl₄]²⁻$[NiCl_4]^{2-}$: Ni²⁺$Ni^{2+}$ (3d⁸$3d^8$) with a weak field ligand (Cl^-$Cl^-$) arrow$\rightarrow$ no pairing occurs arrow$\rightarrow$ tetrahedral profile arrow$\rightarrow$sp³$sp^3$.
(C) [Co(NH₃)₆]³⁺$[Co(NH_3)_6]^{3+}$: Co³⁺$Co^{3+}$ (3d⁶$3d^6$) with a strong field ligand (NH₃$NH_3$) arrow$\rightarrow$ electrons pair up arrow$\rightarrow$ inner orbital configuration arrow$\rightarrow$d²sp³$d^2sp^3$.
(D) [Ni(CN)₄]²⁻$[Ni(CN)_4]^{2-}$: Ni²⁺$Ni^{2+}$ (3d⁸$3d^8$) with a strong field ligand (CN^-$CN^-$) arrow$\rightarrow$ forced pairing opens a 3d$3d$ slot arrow$\rightarrow$ square planar geometry arrow$\rightarrow$dsp²$dsp^2$.
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