Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

Journal Article · Thu Jan 01 00:00:00 EST 2015 · ChemComm

DOI:https://doi.org/10.1039/c4cc05720a· OSTI ID:1241006

Deng, Yi; Zhang, Guanghui; Qi, Xiaotian; Liu, Chao; Miller, Jeffrey T.; Kropf, A. Jeremy; Bunel, Emilio E.; Lan, Yu; Lei, Aiwen

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.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States)
• Sponsoring Organization: National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES); Wuhan University; Argonne National Laboratory - Chemical Sciences and Engineering Division; Chongqing University
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1241006
• Journal Information: ChemComm, Vol. 51, Issue 2; ISSN 1359-7345
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: English