Past exam of the chemistry B course of the University of Cambridge 2023 Paper 2 B6 a i Solution 2026-10-20
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.
Past exam of the chemistry B course of the University of Cambridge 2023 Paper 2 B6 b ii Solution 2026-10-20
cyclohexylamine is expected highest in the spectrochemical series for comparable metal environments. Its alkyl substituent increases the electron-donating ability of nitrogen relative to ammonia, strengthening the sigma interaction and raising the metal–ligand sigma-antibonding levels. The anionic pi donors tend to raise occupied metal levels and give smaller splittings. Steric effects and the metal can modify the exact ordering, so the comparison is a ligand field trend rather than a universal basicity-to-splitting identity.
Past exam of the chemistry B course of the University of Cambridge 2023 Paper 2 B6 b i Solution 2026-10-20
ammonia and cyclohexylamine are sigma-donor ligands; chloride and acetate are sigma- and pi-donor ligands. The nitrogen lone pair of each amine points toward the metal and forms the donor interaction. These saturated amines have no low-lying conjugated acceptor system that would make them conventional pi-acceptor ligands.
chloride uses a lone pair for sigma donation and has additional occupied orbitals perpendicular to the bond that can donate with pi symmetry. An oxygen-bound acetate similarly has occupied oxygen-centred orbitals available for sigma and pi donation, although its carboxylate resonance in chemistry changes their energies and distribution. Neither should be classified as a pi acceptor merely because its bonding can be drawn with multiple bonds or resonance in chemistry contributors. None of these four is a standard sigma-donor/pi-acceptor ligand.