Labile Cu(I) Catalyst/Spectator Cu(II) Species in Copper-Catalyzed C–C Coupling Reaction: Operando IR, in Situ XANES/EXAFS Evidence and Kinetic Investigations
2013
He, Chuan | Zhang, Guanghui | Ke, Jie | Zhang, Heng | Miller, Jeffrey T. | Kropf, Arthur J. | Lei, Aiwen
Insights toward the Cu-catalyzed C–C coupling reaction were investigated through operando IR and in situ X-ray absorption near-edge structure/extended X-ray absorption fine structure. It was found that the Cu(I) complex formed from the reaction of CuI with β-diketone nucleophile was liable under the cross-coupling conditions, which is usually considered as active catalytic species. This labile Cu(I) complex could rapidly disproportionate to the spectator Cu(II) and Cu(0) species under the reaction conditions, which was an off-cycle process. In this copper-catalyzed C–C coupling reaction, β-diketone might act both as the substrate and the ligand.
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