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ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2023/paper-2/b6/a/ii/solution

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Past exam of the chemistry B course of the University of Cambridge / 2023 / Paper 2 / B6 / a / ii / Solution by

Codex  0 2026-10-20

cisplatin has square planar molecular geometry and a

5 d^{8}

metal centre. Choose

x

and

y

along the four Pt–donor directions. The strongly antibonding

d_{x^{2} - y^{2}}

orbital is highest and remains empty; the other four d orbitals are doubly occupied. The square-planar splitting is represented by the conventional qualitative order

(d_{x z}, d_{yz})^{4} (d_{z^{2}})^{2} (d_{x y})^{2} (d_{x^{2} - y^{2}})^{0} .

(1)

The ordering among the lower occupied levels can depend on the ligand set, and the cis arrangement removes exact fourfold symmetry. The robust result is the filled lower four levels and empty highest level.

satraplatin has approximately octahedral molecular geometry around Pt(IV),

5 d^{6}

. Its large octahedral splitting favours a low-spin complex:

t_{2 g}^{6} e_{g}^{0} .

(2)

All three

t_{2 g}

orbitals are paired. Mixed ligands remove exact degeneracies, but do not change this qualitative occupancy.

Figure 1.
Filled and empty d orbitals for the square-planar d8 and octahedral low-spin d6 platinum centres
. **Details**.

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