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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 )

Journal Article · · ChemComm
DOI:https://doi.org/10.1039/c6cc01413e· OSTI ID:1429890
 [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
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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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1429890
Journal Information:
ChemComm, Vol. 52, Issue 42; ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

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