Homolytic cleavage of the O–Cu(II) bond: XAFS and EPR spectroscopy evidence for one electron reduction of Cu(II) to Cu(I)
Hong Yi,a Guanghui Zhang,a Jie Xin,a Yi Deng,a Jeffrey T. Miller,bc Arthur J. Kropf,b Emilio E. Bunel,b Xiaotian Qi,d Yu Lan,d Jyh-Fu Leee and Aiwen Lei*abf
a: College of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Wuhan University, Wuhan, People's Republic of China
d: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
and so on
Chem. Commun., 2016, 52, 6914-6917
DOI: 10.1039/C6CC01413E
Abstract
The investigation into the active copper(I) catalysts from copper(II) precursors has become a fundamental and important task in copper catalysis. In this work, we demonstrate that the tBuO− anion serves not only as a 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.
This process proceeded in DMF, DMA, or NMP (N-methylpyrrolidon), but not in dioxane, THF, or toluene.
a: College of Chemistry and Molecular Sciences, the Institute for Advanced Studies, Wuhan University, Wuhan, People's Republic of China
d: National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
and so on
Chem. Commun., 2016, 52, 6914-6917
DOI: 10.1039/C6CC01413E
Abstract
The investigation into the active copper(I) catalysts from copper(II) precursors has become a fundamental and important task in copper catalysis. In this work, we demonstrate that the tBuO− anion serves not only as a 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.
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