RS‐PS in the Gas Phase—First Generation of (Organothio)thioxophosphanes

A two‐coordinate, trivalent phosphorus atom is present in the title compounds 1 (R  CH3, C6H5), which are formed by electron collision ionization of the corresponding dithiadiphosphetane disulfides 2. Collision activation and neutralization‐reionization mass spectroscopy show that the isomeric dithioxophosphoranes 3 rearrange to 1.