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Title: Homolytic cleavage of the O–Cu( ii ) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu( ii ) to Cu( i )

Abstract

In this work, we demonstrate that the tBuO - anion serves not only as the base but also as a mediator to promote the reduction of Cu(ii) to Cu(i) in copper catalysis. XAFS and EPR spectroscopy evidence the [Cu(O tBu) 3] - ate complex as the key intermediate which undergoes homolytic cleavage of the O–Cu(ii) bond generating [Cu(O tBu) 2] - ate complex.

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [2];  [3];  [3];  [4];  [4];  [5];  [1]
  1. College of Chemistry and Molecular Sciences; the Institute for Advanced Studies; Wuhan University; Wuhan; People's Republic of China
  2. Chemical Sciences and Engineering Division; Argonne National Laboratory; Argonne; USA; School of Chemical Engineering
  3. Chemical Sciences and Engineering Division; Argonne National Laboratory; Argonne; USA
  4. School of Chemistry and Chemical Engineering; Chongqing University; Chongqing 400030; People's Republic of China
  5. National Synchrotron Radiation Research Center; Hsinchu 30076; Taiwan
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1429890
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 52; Journal Issue: 42; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Yi, Hong, Zhang, Guanghui, Xin, Jie, Deng, Yi, Miller, Jeffrey T., Kropf, Arthur J., Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, Lee, Jyh-Fu, and Lei, Aiwen. Homolytic cleavage of the O–Cu( ii ) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu( ii ) to Cu( i ). United States: N. p., 2016. Web. doi:10.1039/c6cc01413e.
Yi, Hong, Zhang, Guanghui, Xin, Jie, Deng, Yi, Miller, Jeffrey T., Kropf, Arthur J., Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, Lee, Jyh-Fu, & Lei, Aiwen. Homolytic cleavage of the O–Cu( ii ) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu( ii ) to Cu( i ). United States. doi:10.1039/c6cc01413e.
Yi, Hong, Zhang, Guanghui, Xin, Jie, Deng, Yi, Miller, Jeffrey T., Kropf, Arthur J., Bunel, Emilio E., Qi, Xiaotian, Lan, Yu, Lee, Jyh-Fu, and Lei, Aiwen. Tue . "Homolytic cleavage of the O–Cu( ii ) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu( ii ) to Cu( i )". United States. doi:10.1039/c6cc01413e.
@article{osti_1429890,
title = {Homolytic cleavage of the O–Cu( ii ) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu( ii ) to Cu( i )},
author = {Yi, Hong and Zhang, Guanghui and Xin, Jie and Deng, Yi and Miller, Jeffrey T. and Kropf, Arthur J. and Bunel, Emilio E. and Qi, Xiaotian and Lan, Yu and Lee, Jyh-Fu and Lei, Aiwen},
abstractNote = {In this work, we demonstrate that the tBuO- anion serves not only as the base but also as a mediator to promote the reduction of Cu(ii) to Cu(i) in copper catalysis. XAFS and EPR spectroscopy evidence the [Cu(OtBu)3]- ate complex as the key intermediate which undergoes homolytic cleavage of the O–Cu(ii) bond generating [Cu(OtBu)2]- ate complex.},
doi = {10.1039/c6cc01413e},
journal = {ChemComm},
issn = {1359-7345},
number = 42,
volume = 52,
place = {United States},
year = {2016},
month = {4}
}

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