Reaction of [Ta(OC6H3Pri2-2,6)3R2] (R=CH2C6H4-4-Me) with H-2 in the presence of phosphine ligands (L) leads to the dihydride compounds [Ta(H)2(OC6H3Pri2-2,6)3(L)], the solid-state structure of the PMe2Ph derivative shows a geometry about the metal centre that is severely distorted from octahedral; hydrogenation of aryl-phosphines and other aromatic substrates is catalysed by these dihydride compounds.