Using the thermally stable salts of [Fe-2(SR)(2)(CO)(3)(PMe3)(dppv)]-BAr4F, we found that the azadithiolates [Fe-2(adtR)(CO)(3)(PMe3)-(dppv)](+) react with high pressures of H-2 to give the hydride [Fe-2(mu-H)(adtR)(CO)(3)(dppv)(PMe3)]BAr4F. The related oxadithiolate and propanedithiolate complexes are unreactive toward H-2. Molecular hydrogen is proposed to undergo heterolysis assisted by the amine followed by isomerization of an initially formed terminal hydride. Use of H-2 and D2O gave the deuteride as well as the hydride, implicating protic intermediates.