cisplatin has square planar molecular geometry and a metal centre. Choose and along the four Pt–donor directions. The strongly antibonding 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
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), . Its large octahedral splitting favours a low-spin complex:
All three 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.
ammonia and cyclohexylamine are neutral donors, whereas each coordinated chloride and acetate has charge . Charge balance therefore gives Pt(II) in cisplatin and Pt(IV) in satraplatin:
The two acetate groups count once each; their carbonyl and alkoxy oxygen atoms do not make each ligand doubly charged.