For the first time, the hydrogenation/hydrogenolysis of a range of disulfides has been achieved over a supported palladium catalyst using hydrogen under relatively benign conditions. These unexpected results demonstrate that it is possible to avoid the poisoning of the catalyst by either the nitrogen-containing groups or the sulfur species, allowing both efficient reaction and recycling of the catalyst under the proper conditions (e.g., at low temperatures). A slight loss in activity was found on recycling; however, the catalyst activity can be recovered using hydrogen pretreatment. The reaction mechanism for the hydrogenolysis and hydrogenation of ortho-, meta-, and para-dinitrodiphenyldisulfide to the corresponding aminothiophenol has been elucidated. Density functional theory calculations were used to investigate the adsorption mode of the dinitrodiphenyldisulfides; a clear dependence on adsorption geometry was found regarding whether the molecule is cleaved at the S-S bond before the reduction of the nitro group or vice versa. This study demonstrates the versatility of these catalysts for the hydrogenation/hydrogenolysis of sulfur-containing molecules, which normally are considered poisons, and will extend their use to a new family of substrates. (C) 2007 Elsevier Inc. All rights reserved.