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• W2007974552 endingPage "3442" @default.
• W2007974552 startingPage "3433" @default.
• W2007974552 abstract "A computational approach (DFT-B3PW91) is used to address previous experimental studies (Chem. Commun. 2009, 6801) that showed that transfer hydrogenation of a cyclic imine by Et3N·HCO2H in dichloromethane catalyzed by 16-electron bifunctional Cp*RhIII(XNC6H4NX′) is faster when XNC6H4NX′ = TsNC6H4NH than when XNC6H4NX′ = HNC6H4NH or TsNC6H4NTs (Cp* = η5-C5Me5, Ts = toluenesulfonyl). The computational study also considers the role of the formate complex observed experimentally at low temperature. Using a model of the experimental complex in which Cp* is replaced by Cp and Ts by benzenesulfonyl (Bs), the calculations for the systems in gas phase reveal that dehydrogenation of formic acid generates CpRhIIIH(XNC6H4NX′H) via an outer-sphere mechanism. The 16-electron Rh complex + formic acid are shown to be at equilibrium with the formate complex, but the latter lies outside the pathway for dehydrogenation. The calculations reproduce the experimental observation that the transfer hydrogenation reaction is fastest for the nonsymmetrically substituted complex CpRhIII(XNC6H4NX′) (X = Bs and X′ = H). The effect of the linker between the two N atoms on the pathway is also considered. The Gibbs energy barrier for dehydrogenation of formic acid is calculated to be much lower for CpRhIII(XNCHPhCHPhNX′) than for CpRhIII(XNC6H4NX′) for all combinations of X and X′. The energy barrier for hydrogenation of the imine by the rhodium hydride complex is much higher than the barrier for hydride transfer to the corresponding iminium ion, in agreement with mechanisms proposed for related systems on the basis of experimental data. Interpretation of the results by MO and NBO analyses shows that the most reactive catalyst for dehydrogenation of formic acid contains a localized Rh–NH π-bond that is associated with the shortest Rh–N distance in the corresponding 16-electron complex. The asymmetric complex CpRhIII(BsNC6H4NH) is shown to generate a good bifunctional catalyst for transfer hydrogenation because it combines an electrophilic metal center and a nucleophilic NH group." @default.
• W2007974552 created "2016-06-24" @default.
• W2007974552 creator A5005296357 @default.
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• W2007974552 creator A5078208746 @default.
• W2007974552 creator A5089726661 @default.
• W2007974552 creator A5091579770 @default.
• W2007974552 date "2014-06-27" @default.
• W2007974552 modified "2023-09-30" @default.
• W2007974552 title "Computational Studies Explain the Importance of Two Different Substituents on the Chelating Bis(amido) Ligand for Transfer Hydrogenation by Bifunctional Cp*Rh(III) Catalysts" @default.
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• W2007974552 doi "https://doi.org/10.1021/om500356e" @default.
• W2007974552 hasPublicationYear "2014" @default.
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