Four chloride ligands give Ti(IV), . Ionic electron counting gives
tetrahedral molecular geometry separates the four donors without placing them at . A centre has no occupied d orbitals providing a square-planar stabilization; the 18-electron rule is not a requirement for this early-metal compound.
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.
Strong ligand-to-metal pi donation is favoured by an occupied ligand p orbital and a suitable empty metal d orbital of matching symmetry, with reasonably similar energies and good spatial overlap. Small donor atoms such as O or N can supply short bonds and efficient overlap; oxo, imido and nitrido ligands are familiar examples. Early transition metals in high oxidation states, often , are particularly favourable because the metal acceptor orbitals are vacant and relatively low in energy. More spatially extended and orbitals can strengthen the overlap.
Metal-to-ligand pi backbonding is the complementary case: electron-rich, low-oxidation-state metals donate occupied d orbitals into low-lying ligand antibonding orbitals, as for CO. In both directions, filling a metal–ligand pi-antibonding orbital offsets the multiple-bond stabilization. The relevant prediction is orbital occupancy and overlap, rather than the presence of a formal double-bond line in a drawing.
A model in which six donor orbitals of an octahedral complex form symmetry-adapted combinations. metal s, p and two d orbitals supply matching symmetry partners; the other three d orbitals remain nonbonding orbitals. The model neglects ligand pi donation, backbonding and departures from octahedral symmetry.
In the ideal tetrahedral point-charge model, the five metal d orbitals split into a lower twofold set and an upper threefold set. Relative to their weighted barycentre their energies are and , where is the separation. For occupancies , the crystal field stabilization energy is . Under weak-field high-spin filling it is , , and zero for respectively. Shorter metal–ligand distances generally increase the splitting, so orbital filling can superimpose nonmonotonic bond-length changes on an ionic-size trend. The model alone does not determine an absolute bond length.