### Core Logic
Let us apply Valence Bond Theory (VBT) and crystal field rules to evaluate each coordination complex:
* **A. [textNi(CO)_4]$[\text{Ni(CO)}_4]$**: Nickel is in the 0$0$ oxidation state (3d^8 4s^2$3d^8 4s^2$). Carbon monoxide (textCO$\text{CO}$) is a strong field ligand, forcing the 4s$4s$ electrons into the 3d$3d$ shell to produce a fully paired 3d^10$3d^{10}$ configuration. The vacant 4s$4s$ and three 4p$4p$ orbitals hybridize into an **sp^3$sp^3$ tetrahedral** geometry. All spins are paired, so mu = 0 text BM$\mu = 0 \text{ BM}$. Thus, textA rightarrow textIII$\text{A} \rightarrow \text{III}$. Valence orbital diagram for nickel tetracarbonyl sp3 system
* **B. [textNi(CN)_4]^2-$[\text{Ni(CN)}_4]^{2-}$**: Nickel is in the +2$+2$ state (3d^8$3d^8$). Cyanide (textCN^-$\text{CN}^-$) is a strong field ligand, forcing the pairing of the two unpaired 3d$3d$ electrons. This leaves one internal 3d$3d$ orbital vacant, leading to **dsp^2$dsp^2$ square planar** hybridization with zero unpaired electrons (mu = 0 text BM$\mu = 0 \text{ BM}$). Thus, textB rightarrow textII$\text{B} \rightarrow \text{II}$. Valence orbital diagram for nickel tetracarbonyl sp3 system
* **C. [textNiCl_4]^2-$[\text{NiCl}_4]^{2-}$**: Nickel is in the +2$+2$ state (3d^8$3d^8$). Chloride (textCl^-$\text{Cl}^-$) is a weak field ligand, leaving the two 3d$3d$ electrons unpaired (n = 2$n = 2$). The system adopts **sp^3$sp^3$ tetrahedral** hybridization with a spin-only moment of mu = sqrt2(2+2) = sqrt8 approx 2.8 text BM$\mu = \sqrt{2(2+2)} = \sqrt{8} \approx 2.8 \text{ BM}$. Thus, textC rightarrow textI$\text{C} \rightarrow \text{I}$. Valence orbital diagram for nickel tetracarbonyl sp3 system
* **D. [textMnBr_4]^2-$[\text{MnBr}_4]^{2-}$**: Manganese is in the +2$+2$ state (3d^5$3d^5$). Bromide (textBr^-$\text{Br}^-$) is a weak field ligand, preserving five unpaired parallel spins (n = 5$n = 5$). The geometry is **sp^3$sp^3$ tetrahedral** with a maximum spin-only moment of mu = sqrt5(5+2) = sqrt35 approx 5.9 text BM$\mu = \sqrt{5(5+2)} = \sqrt{35} \approx 5.9 \text{ BM}$. Thus, textD rightarrow textIV$\text{D} \rightarrow \text{IV}$. Valence orbital diagram for nickel tetracarbonyl sp3 system
### Step 1: Alignment Summary
Consolidating our results:
textA-III, B-II, C-I, D-IV$$\text{A-III, B-II, C-I, D-IV}$$
This matches Option (3).
### Pattern Recognition
Nickel complexes provide classic benchmarks: Nickel zero tetracarbonyl is always tetrahedral diamagnetic. Nickel +2$+2$ tetracyanide is square planar diamagnetic due to strong ligand field pairing. Spotting these properties cuts down the problem solving time significantly.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
Valence orbital diagram for nickel tetracarbonyl sp3 systemValence orbital diagram for nickel tetracarbonyl sp3 systemValence orbital diagram for nickel tetracarbonyl sp3 system
Keywords:#nickel coordination VBT#tetrahedral magnetic moment calculation#square planar diamagnetic complex#JEE Main 2025 Chemistry Q44
More Coordination Compounds Previous-Year Questions — Page 2
Q40jee_main_2025_02_april_morningCrystal Field Theory
Given below are two statements :
Statement (I): In octahedral complexes, when Delta_0 < P$\Delta_0 < P$ high spin complexes are formed. When Delta_0 > P$\Delta_0 > P$ low spin complexes are formed.
Statement (II) : In tetrahedral complexes because of Delta_mathrmt < mathrmP$\Delta_{\mathrm{t}} < \mathrm{P}$, low spin complexes are rarely formed.
In the light of the above statements, choose the most appropriate answer from the options given below:
A.(1)\ textStatement I is correct but Statement II is incorrect.$(1)\ \text{Statement I is correct but Statement II is incorrect.}$
B.(2)\ textBoth Statement I and Statement II are incorrect$(2)\ \text{Both Statement I and Statement II are incorrect}$
C.(3)\ textStatement I is incorrect but Statement II is correct$(3)\ \text{Statement I is incorrect but Statement II is correct}$
D.(4)\ textBoth Statement I and Statement II are correct$(4)\ \text{Both Statement I and Statement II are correct}$
Solution
### Related Formula
Crystal field splitting values relation for matching configuration choices:
Delta_mathrmt = frac49Delta_0$$\Delta_{\mathrm{t}} = \frac{4}{9}\Delta_0$$
### Core Logic
Let's verify both rules based on Crystal Field Theory principles:
* **Statement I**: In octahedral configurations, if pairing penalty energy P$P$ exceeds field split magnitude Delta_0$\Delta_0$, electrons prefer moving to upper sub-shells, creating high-spin states. Conversely, if Delta_0 > P$\Delta_0 > P$, forced pairing occurs, creating low-spin complexes. (Statement I is accurate).
* **Statement II**: Because tetrahedral configurations separate by an extremely narrow gap magnitude Delta_mathrmt$\Delta_{\mathrm{t}}$ (about half of octahedral field splits), the value almost never exceeds standard pairing energy P$P$. Electrons consistently choose higher sub-levels rather than pairing up, meaning low-spin arrangements are extremely rare. (Statement II is accurate).
### Step 1: Verdict
Therefore, both Statement I and Statement II are correct.
### Pattern Recognition
Tetrahedral configurations are systematically assumed to be high-spin unless special structural properties dictate otherwise, due to the Delta_mathrmt < P$\Delta_{\mathrm{t}} < P$ constraint.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
Qjee_main_2025_03_april_eveningMagnetic Properties and Hybridization of Complexes
Identify the diamagnetic octahedral complex ions from below;
A. [mathrmMn(mathrmCN)_6]^3-$[\mathrm{Mn}(\mathrm{CN})_6]^{3-}$
B. [mathrmCo(mathrmNH_3)_6]^3+$[\mathrm{Co}(\mathrm{NH}_3)_6]^{3+}$
C. [mathrmFe(mathrmCN)_6]^4-$[\mathrm{Fe}(\mathrm{CN})_6]^{4-}$
D. [mathrmCo(mathrmH_2mathrmO)_3mathrmF_3]$[\mathrm{Co}(\mathrm{H}_2\mathrm{O})_3\mathrm{F}_3]$
Choose the correct answer from the options given below :
A. B and D Only
B. A and D Only
C. A and C Only
D. B and C Only
Solution
### Related Formula
According to Crystal Field Theory (CFT):
- A complex is diamagnetic if all electrons are paired up (unpaired electrons, n=0$n=0$).
- Strong field ligands (like mathrmCN^-$\mathrm{CN}^-$, mathrmNH_3$\mathrm{NH}_3$ with Co^3+$Co^{3+}$) cause pairing of electrons if Delta_o > P$\Delta_o > P$.
{{SOLUTION_IMG}}
### Core Logic
Analyze each complex:
- **A. [mathrmMn(mathrmCN)_6]^3-$[\mathrm{Mn}(\mathrm{CN})_6]^{3-}$**:
- Mn^3+$Mn^{3+}$ has d^4$d^4$ configuration.
- Strong field ligand mathrmCN^-$\mathrm{CN}^-$ causes pairing in t_2g$t_{2g}$ orbitals: t_2g^4 e_g^0$t_{2g}^4 e_g^0$.
- There are 2 unpaired electrons rightarrow$\rightarrow$ *Paramagnetic*.
- **B. [mathrmCo(mathrmNH_3)_6]^3+$[\mathrm{Co}(\mathrm{NH}_3)_6]^{3+}$**:
- Co^3+$Co^{3+}$ has d^6$d^6$ configuration.
- mathrmNH_3$\mathrm{NH}_3$ acts as strong field ligand with Co^3+$Co^{3+}$, causing complete pairing: t_2g^6 e_g^0$t_{2g}^6 e_g^0$.
- No unpaired electrons rightarrow$\rightarrow$ *Diamagnetic*.
### Step 1: Analyze complexes C and D
- **C. [mathrmFe(mathrmCN)_6]^4-$[\mathrm{Fe}(mathrm{CN})_6]^{4-}$**:
- Fe^2+$Fe^{2+}$ has d^6$d^6$ configuration.
- Strong field ligand mathrmCN^-$\mathrm{CN}^-$ causes complete pairing: t_2g^6 e_g^0$t_{2g}^6 e_g^0$.
- No unpaired electrons rightarrow$\rightarrow$ *Diamagnetic*.
- **D. [mathrmCo(mathrmH_2mathrmO)_3mathrmF_3]$[\mathrm{Co}(\mathrm{H}_2\mathrm{O})_3\mathrm{F}_3]$**:
- Co^3+$Co^{3+}$ has d^6$d^6$ configuration.
- Weak field ligands (mathrmF^-$\mathrm{F}^-$, mathrmH_2mathrmO$\mathrm{H}_2\mathrm{O}$) do not cause pairing: t_2g^4 e_g^2$t_{2g}^4 e_g^2$.
- There are 4 unpaired electrons rightarrow$\rightarrow$ *Paramagnetic*.
### Step 2: Conclusion
Only complexes B and C are diamagnetic, matching Option (4).
### Pattern Recognition
Octahedral d^6$d^6$ ions (such as Co^3+$Co^{3+}$ or Fe^2+$Fe^{2+}$) coupled with strong-field ligands are exceptionally stable and always form low-spin, fully paired, diamagnetic complexes (t_2g^6 e_g^0$t_{2g}^6 e_g^0$).
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
Q44jee_main_2025_07_april_morningIsomerism in Coordination Compounds
An octahedral complex having molecular composition mathrmCo cdot 5NH_3 cdot Cl cdot SO_4$\mathrm{Co \cdot 5NH_3 \cdot Cl \cdot SO_4}$ has two isomers A and B. The solution of A gives a white precipitate with mathrmAgNO_3$\mathrm{AgNO_3}$ solution and the solution of B gives a white precipitate with mathrmBaCl_2$\mathrm{BaCl_2}$ solution. The type of isomerism exhibited by the complex is:
### Core Logic
The complex molecular composition is mathrmCo cdot 5NH_3 cdot Cl cdot SO_4$\mathrm{Co \cdot 5NH_3 \cdot Cl \cdot SO_4}$. Let's formulate the formulas for the two isomers:
1. **Isomer A**: Gives a white precipitate of mathrmAgCl$\mathrm{AgCl}$ when reacted with mathrmAgNO_3$\mathrm{AgNO_3}$. This means free chloride ions (mathrmCl^-$\mathrm{Cl}^-$) are present in the outer ionization sphere:
[mathrmCo(NH_3)_5(SO_4)]mathrmCl$$[\mathrm{Co(NH_3)_5(SO_4)}]\mathrm{Cl}$$
2. **Isomer B**: Gives a white precipitate of mathrmBaSO_4$\mathrm{BaSO_4}$ when reacted with mathrmBaCl_2$\mathrm{BaCl_2}$. This means free sulphate ions (mathrmSO_4^2-$\mathrm{SO}_4^{2-}$) are present in the outer ionization sphere:
[mathrmCo(NH_3)_5Cl]mathrmSO_4$$[\mathrm{Co(NH_3)_5Cl}]\mathrm{SO_4}$$
Since these two isomers yield different ions in solution due to exchange of ligands between the coordination sphere and the ionization sphere, they exhibit **Ionisation isomerism**.
### Pattern Recognition
Test for ions:
- mathrmAgNO_3$\mathrm{AgNO_3}$ PPT rightarrow$\rightarrow$ free halide ion in outer sphere.
- mathrmBaCl_2$\mathrm{BaCl_2}$ PPT rightarrow$\rightarrow$ free sulphate ion in outer sphere.
- Outer-inner ion exchanges are always called **Ionisation isomerism**.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
Q50jee_main_2025_07_april_morningValence Bond Theory
The number of paramagnetic complexes among [mathrmFeF_6]^3-$[\mathrm{FeF}_{6}]^{3-}$, [mathrmFe(CN)_6]^3-$[\mathrm{Fe(CN)}_{6}]^{3-}$, [mathrmMn(CN)_6]^3-$[\mathrm{Mn(CN)}_{6}]^{3-}$, [mathrmCo(C_2mathrmO_4)_3]^3-$[\mathrm{Co(C}_{2}\mathrm{O}_{4})_{3}]^{3-}$, [mathrmMnCl_6]^3-$[\mathrm{MnCl}_{6}]^{3-}$ and [mathrmCoF_6]^3-$[\mathrm{CoF}_{6}]^{3-}$, which involve mathrmd^2mathrmsp^3$\mathrm{d}^{2}\mathrm{sp}^{3}$ hybridization is ______.
Numerical Answer.Answer: 2 to 2
Solution
### Core Logic
Let's systematically analyze the coordination, ligand strength, hybridization, and magnetic behavior of each complex:
1. **[mathrmFeF_6]^3-$[\mathrm{FeF}_{6}]^{3-}$**:
- mathrmFe^3+$\mathrm{Fe}^{3+}$ (3mathrmd^5$3\mathrm{d}^5$). mathrmF^-$\mathrm{F}^-$ is a weak-field ligand (WFL). No pairing occurs.
- Outer-orbital complex: mathrmsp^3mathrmd^2$\mathrm{sp}^3\mathrm{d}^2$.
- Paramagnetic (5$5$ unpaired electrons).
2. **[mathrmFe(CN)_6]^3-$[\mathrm{Fe(CN)}_{6}]^{3-}$**:
- mathrmFe^3+$\mathrm{Fe}^{3+}$ (3mathrmd^5$3\mathrm{d}^5$). mathrmCN^-$\mathrm{CN}^-$ is a strong-field ligand (SFL). Pairing occurs.
- Config: mathrmt_2mathrmg^5\ mathrme_mathrmg^0$\mathrm{t}_{2\mathrm{g}}^5\ \mathrm{e}_{\mathrm{g}}^0$ (one unpaired electron remains implies$\implies$ **Paramagnetic**).
- Inner-orbital complex: **mathrmd^2mathrmsp^3$\mathrm{d}^2\mathrm{sp}^3$**.
3. **[mathrmMn(CN)_6]^3-$[\mathrm{Mn(CN)}_{6}]^{3-}$**:
- mathrmMn^3+$\mathrm{Mn}^{3+}$ (3mathrmd^4$3\mathrm{d}^4$). mathrmCN^-$\mathrm{CN}^-$ is an SFL. Pairing occurs.
- Config: mathrmt_2mathrmg^4\ mathrme_mathrmg^0$\mathrm{t}_{2\mathrm{g}}^4\ \mathrm{e}_{\mathrm{g}}^0$ (two unpaired electrons remain implies$\implies$ **Paramagnetic**).
- Inner-orbital complex: **mathrmd^2mathrmsp^3$\mathrm{d}^2\mathrm{sp}^3$**.
4. **[mathrmCo(C_2mathrmO_4)_3]^3-$[\mathrm{Co(C}_2\mathrm{O}_4)_3]^{3-}$**:
- mathrmCo^3+$\mathrm{Co}^{3+}$ (3mathrmd^6$3\mathrm{d}^6$). Oxalate is a chelating SFL here. Full pairing occurs.
- Config: mathrmt_2mathrmg^6\ mathrme_mathrmg^0$\mathrm{t}_{2\mathrm{g}}^6\ \mathrm{e}_{\mathrm{g}}^0$ (zero unpaired electrons implies$\implies$ Diamagnetic).
- Inner-orbital complex: mathrmd^2mathrmsp^3$\mathrm{d}^2\mathrm{sp}^3$.
5. **[mathrmMnCl_6]^3-$[\mathrm{MnCl}_{6}]^{3-}$**:
- mathrmMn^3+$\mathrm{Mn}^{3+}$ (3mathrmd^4$3\mathrm{d}^4$). mathrmCl^-$\mathrm{Cl}^-$ is a WFL. No pairing occurs.
- Outer-orbital complex: mathrmsp^3mathrmd^2$\mathrm{sp}^3\mathrm{d}^2$.
- Paramagnetic (4$4$ unpaired electrons).
6. **[mathrmCoF_6]^3-$[\mathrm{CoF}_{6}]^{3-}$**:
- mathrmCo^3+$\mathrm{Co}^{3+}$ (3mathrmd^6$3\mathrm{d}^6$). mathrmF^-$\mathrm{F}^-$ is a WFL. No pairing occurs.
- Outer-orbital complex: mathrmsp^3mathrmd^2$\mathrm{sp}^3\mathrm{d}^2$.
- Paramagnetic (4$4$ unpaired electrons).
Thus, only [mathrmFe(CN)_6]^3-$[\mathrm{Fe(CN)}_{6}]^{3-}$ and [mathrmMn(CN)_6]^3-$[\mathrm{Mn(CN)}_{6}]^{3-}$ are both **paramagnetic** and involve **mathrmd^2mathrmsp^3$\mathrm{d}^2\mathrm{sp}^3$** hybridization.
### Pattern Recognition
VBT shortcut:
- Strong-field ligand complexes with d^4text--d^6$d^4\text{--}d^6$ central ions form inner-orbital mathrmd^2mathrmsp^3$\mathrm{d}^2\mathrm{sp}^3$ complexes.
- Of those, check the number of electrons: d^6$d^6$ is completely paired (diamagnetic), but d^5$d^5$ ([Fe(CN)_6]^3-$[Fe(CN)_6]^{3-}$) and d^4$d^4$ ([Mn(CN)_6]^3-$[Mn(CN)_6]^{3-}$) both leave unpaired electrons in the t_2g$t_{2g}$ orbitals (paramagnetic).
### Evaluation Rubric / Model Answer
Detailed individual classification of each complex based on VBT/CFT to yield the correct count of 2$2$ inner-orbital paramagnetic complexes.
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
Q31jee_main_2025_08_april_eveningIsomerism in Coordination Compounds
Given below are two statements:
Statement I: A homoleptic octahedral complex, formed using monodentate ligands, will not show stereoisomerism.
Statement II: cis- and trans-platin are heteroleptic complexes of Pd.
In the light of the above statements, choose the correct answer from the options given below:
A.textBoth Statement I and Statement II are false.$\text{Both Statement I and Statement II are false.}$
B.textStatement I is false but Statement II is true.$\text{Statement I is false but Statement II is true.}$
C.textBoth Statement I and Statement II are true.$\text{Both Statement I and Statement II are true.}$
D.textStatement I is true but Statement II is false.$\text{Statement I is true but Statement II is false.}$
Solution
### Core Logic
Let us evaluate both statements individually:
* **Statement I**: A homoleptic complex contains only one type of ligand. For an octahedral complex using monodentate ligands, the general formula is [Ma_6]$[Ma_6]$. Since all coordination positions are populated identically by the exact same ligand, swapping spatial positions produces no structural difference, hence it cannot demonstrate geometrical or optical isomerism. **Statement I is true.** Stereochemical representation of octahedral homoleptic system
* **Statement II**: Cis-platin and trans-platin have the chemical formula [Pt(NH_3)_2Cl_2]$[Pt(NH_3)_2Cl_2]$. While they are indeed heteroleptic complexes, they are coordination coordinates of **Platinum (Pt$Pt$)**, not Palladium (Pd$Pd$). **Statement II is false.** Stereochemical representation of octahedral homoleptic system
### Pattern Recognition
Always read element symbols with immense focus in coordination chemistry. Changing a single letter from Pt to Pd creates a false assertion trap designed to test parsing alertness rather than chemical difficulty.
### Evaluation Rubric / Model Answer
null
### Chapter Mix
Class 12 Chemistry: Coordination Compounds
More Coordination Compounds Questions — jee_main_2025_08_april_evening
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