The Rh(III) complexes [((t)bpy)(2)Rh(OMe)(L)]-[X] [X](n) ((t)bpy) = 4,4'-di-tert-butyl-2,2'-bipyridyl; L = MeOH, n = 2, X = OTf (OTf = trifluoromethanesulfonate), TFA (TFA = trifluoroacetate); L = TFA, n = 1, X = OTf) have been shown to activate dihydrogen via net 1,2-addition of the H H bond across the Rh-III-OMe bond. The bis(methoxide) complex [((t)bPY)(2)Rh(OMe)(2)][OTf] was synthesized by addition of CsOH center dot H2O in methanol to [((t)bPY)(2)Rh(OTf)(2)[OTf] in CH3CN. The addition of HTFA to [((t)bpy)(2)Rh(OMe)(2)][OTf] leads to the formation of [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA], which exists in equilibrium with [((t)bpy)(2)Rh(OMe)(TFA)][OTf]. The mixture of [((t)bpy)(2)Rh(OMe)(MeOH)] [OTf][TFA] and [((t)bpy)(2)Rh(OMe)(TFA)][OTf] activates dihyclrogen at 68 degrees C to give methanol and [((t)bpy)(2)Rh(H)(TFA)][OTf]. Studies indicate that the activation of dihydrogen has a first-order dependence on the Rh(III) methoxide complex and a dependence on hydrogen that is between zero and first order. Combined experimental and computational studies have led to a proposed mechanism for hydrogen activation by [((t)bpy)(2)Rh(OMe)(MeOH)][OTf][TFA] that involves dissociation of Me0H, coordination of hydrogen, and 1,2-addition of hydrogen across the Rh OMe bond. DFT calculations indicate that there is a substantial energy penalty for MeOH dissociation and a relatively flat energy surface for subsequent hydrogen coordination and activation.