S,S'-(Diphenylstannylene) O,O,O',O'-tetraaryl bis[phosphorodithioates] (= [(diphenylstannylene)bis(thio)]bis[bis(aryloxy)phosphine P-sulfides]) 5 react with N-iodosuccinimide (NIS) in CH2Cl2 at -30degrees under A to give 'bis(aryloxy)phosphorothioylsulfenyl iodides' (=bis(aryloxy)phosphinesulfenyl iodide P-sulfides) 6 (Scheme 3), which can readily react in situ with 4-methylbenzenecarbodithioic acid, thiol, and cyclohexene to afford the corresponding unsymmetrical disulfides and the adduct in good yields as the novel electrophilic dithiophosphorylating reagents (Schemes 4 and 5). By adding hexane into the solution at -30degrees after reaction of 5 with NIS, the 'phosphorothioylsulfenyl iodides' 6 can be isolated as yellow solids in good yields (see Table).