We report a neutron diffraction study of the liquid structure of YCl₃ and combine the structural data with macroscopic melting and transport data to contrast the behaviour of this molten salt with those of SrCl₂, ZnCl₂ and AlCl₃ as prototypes of different melting mechanisms for ionic materials. A novel melting mechanism for trivalent metal chlorides, leading to a loose disordered network of edge-sharing octahedral units in the liquid phase, is thereby established. The various melting behaviours are related to bonding character with the help of Pettifor's phenomenological chemical scale.