The structure commonly occurs for d0, d1 and d2 transition metal complexes with covalently-bound ligands and small charge separation.

Furthermore, when unoccupied, said orbital participates in bonding and causes C3v distortion, like in W(CH3)6.

[2] The figure shows the six carbon atoms arranged at the vertices of a triangular prism with the tungsten at the centre.

Some other transition metals have trigonal prismatic hexamethyl complexes, including both neutral molecules such as Mo(CH3)6 and Re(CH3)6 and ions such as Ta(CH3)−6 and Zr(CH3)2−6.

[3] The complex Mo(S−CH=CH−S)3 is also trigonal prismatic, with each S−CH=CH−S group acting as a bidentate ligand with two sulfur atoms binding the metal atom.