Solution

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

The more radially extended Pt orbitals give strong metal–ligand overlap and covalent bonding. This helps compensate the energetic cost of reaching Pt(IV), and the large octahedral ligand field splitting strongly stabilizes its low-spin configuration, with a crystal field stabilization energy contribution before separately counting pairing and the full bond energies. Ni bonding is less effective in this respect; Pd compounds also generally favour the very stable M(II) arrangement more strongly than Pt does. The stronger bonding and large ligand-field stabilization available to Pt(IV) make oxidation to more favourable relative to its congeners. This is a comparative trend, not a claim that Ni(IV) or Pd(IV) complexes cannot exist.

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