168750 20260217214838.0 doi 10.1021/ic500636m sideral 148120 ART-2014-148120 eng Burgess, Samantha A. 1,2-Addition of Dihydrogen across Rhodium(III)–OMe Bonds 2014 The 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. info:eu-repo/semantics/closedAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.762 2014 CHEMISTRY, INORGANIC & NUCLEAR 4 / 45 = 0.089 2014 Q1 T1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Devarajan, Deepa Bolaño, Tamara Universidad de Zaragoza (orcid)0000-0001-8977-6734 Ess, Daniel H. Gunnoe, T. Brent Sabat, Michal Myers, William H. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 53, 10 (2014), 5328-5340 Inorg. chem. Inorganic Chemistry 0020-1669 2660588 http://zaguan.unizar.es/record/168750/files/texto_completo.pdf Versión publicada 3120579 http://zaguan.unizar.es/record/168750/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:168750 articulos driver 2026-02-17-20:14:53 ARTICLE