Stereoisomerisation interconverting different or equivalent spatial arrangements of ligands about a central atom or of a cage of atoms, where the ligand or cage defines the vertices of a polyhedron. For example pyramidal inversion of amines, Berry pseudorotation of PF5, rearrangements of polyhedral boranes. See E. L. Muetterties, J. Am. Chem. Soc. 91, 1636-1643 (1969).
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