Reaction Pathways and Energetics of Etheric C–O Bond Cleavage Catalyzed by Lanthanide Triflates

Abstract

Efficient and selective cleavage of etheric C–O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln­(OTf)₃, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C–O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C–O cleavage occurs via a C–H → O–H proton transfer in concert with weakening of the C–O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb­(OTf)₃-catalyzed ring opening are explored in depth, and for 1-methyl-<i>d</i>₃-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C–O bond scission processes increasing the degrees of freedom/particles as the transition state is approached