Two new heterocyclic thiophosphoryl chlorides (2), derivatives of 1,3,2-benzodiazaphosphole, are synthesized. The reaction of respective thiophospboryl chlorides (1) and (2) with AlCl3 affords dimeric heterocyclic diphosphonium dications 3 and 4. The reaction of 2a with CF3SO3Ag gives rise to dimeric anhydride 5 instead of the expected lambda(5)sigma(3)-thiophosphoryl cations. The results show that lambda(5)sigma(3)-thiophosphonium cations incorporated into a thiadiaza-phospholic system (1) or benzodiazaphospholic system (2) are not stable, and undergo a structural...
