JEE AdvancedChemistryCoordination CompoundsMultiple correct+4 / −2
The complex(es), which can exhibit the type of isomerism shown by , is(are) : [en ]
- A
- B
- C
- D
View written solutionFree
Correct answer: C, D
Step-by-step Derivations:
-
Analyze the reference complex
[Pt(NH₃)₂Br₂]to determine the type of isomerism it exhibits.- The central metal ion is Pt²⁺. Pt(II) complexes with a coordination number of 4 are typically square planar.
- The complex has the general formula
[MA₂B₂], where M = Pt, A = NH₃, and B = Br⁻. - Square planar complexes of the type
[MA₂B₂]can exist as two different geometrical isomers:cisandtrans.- In the
cis-isomer, the two identical ligands (e.g., NH₃) are adjacent to each other (at 90°). - In the
trans-isomer, the two identical ligands are opposite to each other (at 180°).
- In the
- Therefore,
[Pt(NH₃)₂Br₂]exhibits geometrical (cis-trans) isomerism. - The task is to identify which of the given options also exhibit this type of isomerism.
-
Evaluate each option:
-
A:
[Pt(en)(SCN)₂]- This is a Pt(II) complex, so it is square planar.
- It contains a bidentate ligand, ethylenediamine (en), and two monodentate ligands, thiocyanate (SCN⁻).
- The formula type is
[M(AA)B₂]where (AA) is the bidentate ligand. - In a square planar complex, the bidentate ligand
enmust occupy two adjacent positions. Consequently, the twoSCN⁻ligands must also occupy the remaining two adjacent positions. There is only one possible spatial arrangement, so this complex does not show geometrical isomerism. - However,
SCN⁻is an ambidentate ligand and can coordinate through either S (thiocyanato) or N (isothiocyanato), leading to linkage isomerism. This is a different type of isomerism. Thus, A is incorrect.
-
B:
[Zn(NH₃)₂Cl₂]- The central metal ion is Zn²⁺, which has a
d¹⁰electronic configuration. - Zn(II) complexes with coordination number 4 are tetrahedral.
- In a tetrahedral geometry, all four ligand positions are equivalent with respect to each other (all angles are 109.5°). Therefore, changing the positions of ligands does not create a new isomer. Tetrahedral complexes of the type
[MA₂B₂]do not exhibit geometrical isomerism. - Thus, B is incorrect.
- The central metal ion is Zn²⁺, which has a
-
C:
[Pt(NH₃)₂Cl₄]- The central metal ion is Pt⁴⁺. Pt(IV) complexes with a coordination number of 6 are octahedral.
- The complex has the general formula
[MA₂B₄]where M = Pt, A = NH₃, and B = Cl⁻. - Octahedral complexes of this type exhibit geometrical isomerism based on the relative positions of the two 'A' ligands.
cis-isomer: The two NH₃ ligands are adjacent (90° apart).trans-isomer: The two NH₃ ligands are opposite (180° apart).
- Since this complex shows geometrical isomerism, C is correct.
-
D:
[Cr(en)₂(H₂O)(SO₄)]⁺- The central metal ion is Cr³⁺. Cr(III) complexes with a coordination number of 6 are octahedral.
- The ligands are two bidentate
en, one monodentateH₂O, and one monodentateSO₄²⁻. The coordination number is 2×2 + 1 + 1 = 6. - The complex has the general formula
[M(AA)₂BC]. - Octahedral complexes of this type exhibit geometrical isomerism. The two
enligands can be arrangedcisortransto each other. This arrangement dictates the relative positions of the monodentate ligandsH₂OandSO₄²⁻.cis-isomer: The twoenligands are adjacent. The remaining two positions are also adjacent, soH₂OandSO₄²⁻arecisto each other.trans-isomer: The four N donor atoms from the twoenligands lie in a plane. TheH₂OandSO₄²⁻ligands occupy the axial positions, making themtransto each other.
- Since the complex can exist as
cisandtransisomers, it exhibits geometrical isomerism. Thus, D is correct.
-
Conclusion:
Both complexes [Pt(NH₃)₂Cl₄] and [Cr(en)₂(H₂O)(SO₄)]⁺ exhibit geometrical isomerism, which is the same type of isomerism shown by the reference complex [Pt(NH₃)₂Br₂]. Therefore, options C and D are the correct answers.
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