Hydrolytically stable silanethiol tris(2,6-diisopropylphenoxy)silanethiol (TDST) has been synthesized and reacted with sodium metal. In solid state TDST exhibits pi-interactions between the S-H unit and the pi-system of the arene, replaced by cation-pi interactions in its sodium salts. The interactions are documented by crystal structures and FT-IR spectroscopy.