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

机译:镧系元素三氟甲磺酸酯催化醚键C-O键断裂的反应途径和能量

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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-d3-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.
机译:醚键C-O键的有效和选择性裂解对于将生物质转化为平台化学品和液体运输燃料至关重要。在此贡献中,采用DFT B3LYP理论水平的计算方法来了解三氟化镧催化剂(Ln(OTf)3,Ln = La,Ce,Sm,Gd,Yb和Lu)裂解醚性CO键的功效。与实验一致,计算表明C-O裂解的反应途径是通过C→H→O→H质子转移而发生的,与配位醚底物的C-O键的减弱相结合,最终产生配位的链烯醇。该过程的活化能随镧系元素离子半径的减小而下降,反映出增强的金属离子亲电性。深入探讨了Yb(OTf)3催化的开环反应机理的细节,对于1-甲基-d3-丁基苯基醚,计算得出的2.4的一级动力学同位素效应与实验(2.7)非常吻合,证实了醚的开环途径涉及质子从甲基基团转移到醚氧原子上,该氧原子被亲电子镧系元素离子激活。使用八种不同的醚底物对催化途径的计算表明,无环醚与环状醚的裂解速度更快,这在很大程度上是由于熵的作用,随着接近过渡态,前者的C-O键断裂过程增加了自由度/颗粒的程度。

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