The synthesis of 1,3,5-tris(dimethylamino)benzene (5, Ar-H) is reported. The x-ray structure of 5 reveals two independent mols. in the unit cell both contg. planar arene rings; the puckering of the amino substituents is demonstrated to be a consequence of steric interactions. 5 Is metalated by BuLi to give the isolable aryllithium compd. ArLi (6) from which the phosphine ArPCl2 (7) and silane ArSiCl3 (8) are obtained.