CT.* 1Tariotis room -temperature -stable monoorganylpolysulfanides of the form [X] [RS] (X = [PPI14]+, [PNP], [1\TEt4]+; R = Ph, t- opha+, Bu, n > 2) were synthesized in a simple and versatile one-step process PNP*, starting from sodium thiolates and elemental sulfur. The compounds NEt4 ere characterized by X-ray crystal structure analysis, NMR spectroscopy, microeiemental analysis, and electrospray mass ionization S spectrometry including collision -induced dissociation experiments. O'Pti.., PPha.While these salts are well-defined species as crystals, they undergo Cooled R.T. aftercomplex equilibria in solution. In one case, compounds ranging from rt -7 (LN2} heat gun 1-8 have been observed in solution. Structural features, dynamics in solution, as well as thermochrornic properties of one density decomposition analyses.