000168750 001__ 168750 000168750 005__ 20260217214838.0 000168750 0247_ $$2doi$$a10.1021/ic500636m 000168750 0248_ $$2sideral$$a148120 000168750 037__ $$aART-2014-148120 000168750 041__ $$aeng 000168750 100__ $$aBurgess, Samantha A. 000168750 245__ $$a1,2-Addition of Dihydrogen across Rhodium(III)–OMe Bonds 000168750 260__ $$c2014 000168750 5203_ $$aThe Rh(III) complexes [(tbpy)2Rh(OMe)(L)][X]n (tbpy = 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 RhIII–OMe bond. The bis(methoxide) complex [(tbpy)2Rh(OMe)2][OTf] was synthesized by addition of CsOH·H2O in methanol to [(tbpy)2Rh(OTf)2][OTf] in CH3CN. The addition of HTFA to [(tbpy)2Rh(OMe)2][OTf] leads to the formation of [(tbpy)2Rh(OMe)(MeOH)][OTf][TFA], which exists in equilibrium with [(tbpy)2Rh(OMe)(TFA)][OTf]. The mixture of [(tbpy)2Rh(OMe)(MeOH)][OTf][TFA] and [(tbpy)2Rh(OMe)(TFA)][OTf] activates dihydrogen at 68 °C to give methanol and [(tbpy)2Rh(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 [(tbpy)2Rh(OMe)(MeOH)][OTf][TFA] that involves dissociation of MeOH, 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. 000168750 540__ $$9info:eu-repo/semantics/closedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/ 000168750 590__ $$a4.762$$b2014 000168750 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b4 / 45 = 0.089$$c2014$$dQ1$$eT1 000168750 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000168750 700__ $$aDevarajan, Deepa 000168750 700__ $$0(orcid)0000-0001-8977-6734$$aBolaño, Tamara$$uUniversidad de Zaragoza 000168750 700__ $$aEss, Daniel H. 000168750 700__ $$aGunnoe, T. Brent 000168750 700__ $$aSabat, Michal 000168750 700__ $$aMyers, William H. 000168750 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000168750 773__ $$g53, 10 (2014), 5328-5340$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669 000168750 8564_ $$s2660588$$uhttps://zaguan.unizar.es/record/168750/files/texto_completo.pdf$$yVersión publicada 000168750 8564_ $$s3120579$$uhttps://zaguan.unizar.es/record/168750/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000168750 909CO $$ooai:zaguan.unizar.es:168750$$particulos$$pdriver 000168750 951__ $$a2026-02-17-20:14:53 000168750 980__ $$aARTICLE