Question 37

Among (a) - (d), the complexes that can show geometrical isomerism are:
(a) [Pt(NH$$_3$$)$$_3$$Cl]$$^+$$
(b) [Pt(NH$$_3$$)Cl$$_5$$]$$^-$$
(c) [Pt(NH$$_3$$)$$_2$$Cl(NO$$_2$$)]
(d) [Pt(NH$$_3$$)$$_4$$ClBr]$$^{2+}$$

We begin by noting that platinum generally forms square-planar complexes in the +2 oxidation state ($$d^8$$) and octahedral complexes in the +4 oxidation state ($$d^6$$). Counting the ligands in each formula will therefore tell us the geometry and hence whether geometrical (cis-trans) isomerism is possible.

(a) $$[{\rm Pt(NH_3)_3Cl}]^{+}$$
The complex contains four ligands, so the Pt is $$+2$$ and the geometry is square planar. Its empirical type is $$MA_3B$$ where $$A = NH_3$$ and $$B = Cl^-$$. For a square-planar $$MA_3B$$ ion, placing the single $$B$$ ligand at any one of the four corners and then simply rotating the square makes all arrangements equivalent. Hence there is only one possible arrangement and no cis-trans pair can arise. So, no geometrical isomerism.

(b) $$[{\rm Pt(NH_3)Cl_5}]^{-}$$
Here we have six ligands in all, so Pt must be $$+4$$ and the geometry is octahedral. The formulation is $$AB_5$$ with $$A = NH_3$$ and $$B = Cl^-$$. In an octahedron having five identical ligands and one different ligand, whichever position the single $$A$$ occupies, all five $$B$$ ligands remain equivalent by symmetry; consequently there is still only one possible arrangement. Thus, no geometrical isomerism can occur.

(c) $$[{\rm Pt(NH_3)_2Cl(NO_2)}]$$
This complex has four ligands, giving a square-planar $$+2$$ species. Its type is $$MA_2BC$$ with the identical ligands $$A = NH_3$$. For a square-planar $$MA_2BC$$ complex, the two identical $$A$$ ligands may lie adjacent (cis) or opposite (trans). Hence two distinct geometrical isomers (cis and trans) are possible.

(d) $$[{\rm Pt(NH_3)_4ClBr}]^{2+}$$
There are six ligands, so again Pt is $$+4$$ and the geometry is octahedral. The pattern is $$MA_4BC$$ where $$A = NH_3,\; B = Cl^-,\; C = Br^-$$. In an octahedron of type $$MA_4BC$$ the two different ligands ($$B$$ and $$C$$) can be placed either cis (adjacent) or trans (opposite) to each other, producing two geometrical isomers.

Summarising these results:
$$[{\rm Pt(NH_3)_3Cl}]^{+}$$ - no isomerism;
$$[{\rm Pt(NH_3)Cl_5}]^{-}$$ - no isomerism;
$$[{\rm Pt(NH_3)_2Cl(NO_2)}]$$ - shows geometrical isomerism;
$$[{\rm Pt(NH_3)_4ClBr}]^{2+}$$ - shows geometrical isomerism.

Therefore the complexes capable of geometrical isomerism are (c) and (d).

Hence, the correct answer is Option C.

Was this solution helpful?

Get AI Help

Video Solution

video

Create a FREE account and get:

  • Free JEE Mains Previous Papers PDF
  • Take JEE Mains paper tests
Ask AI