Deng Yi, Zhang Guanghui, Qi Xiaotian, Liu Chao, Miller Jeffrey T, Kropf A Jeremy, Bunel Emilio E, Lan Yu, Lei Aiwen
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, China.
Chem Commun (Camb). 2015 Jan 7;51(2):318-21. doi: 10.1039/c4cc05720a. Epub 2014 Nov 13.
In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(i) to Cu(ii) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI-TMEDA involves a side-on transition state, while oxidation of CuCl-TMEDA involves an end-on transition state which has a lower activation energy.
原位红外（IR）和X射线吸收近边结构（XANES）光谱研究表明，在四甲基乙二胺（TMEDA）存在的情况下，不同的卤化物配体对Cu（I）有氧氧化为Cu（II）具有不同的影响。碘化物配体的反应速率最低，因此导致对苯二酚有氧氧化为苯醌的催化反应速率最低。进一步的密度泛函理论（DFT）计算表明，CuI-TMEDA的氧化涉及侧接过渡态，而CuCl-TMEDA的氧化涉及具有较低活化能的端接过渡态。
