Past exam of the chemistry B course of the University of Cambridge / 2023 / Paper 2 / B6 / d

The more radially extended Pt $5d$ 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 $d^6$ configuration, with a crystal field stabilization energy contribution $-2.4{\Delta }_o$ before separately counting pairing and the full bond energies. Ni $3d$ bonding is less effective in this respect; Pd $4d$ compounds also generally favour the very stable $d^8$ M(II) arrangement more strongly than Pt does. The stronger bonding and large ligand-field stabilization available to Pt(IV) make oxidation to $+4$ more favourable relative to its congeners. This is a comparative trend, not a claim that Ni(IV) or Pd(IV) complexes cannot exist.