title: Mechanism of Synergistic Cu(II)/Cu(I)-Mediated Alkyne Coupling: Dinuclear 1,2-Reductive Elimination after Minimum Energy Crossing Point.
abstract: An in-depth theoretical study of synergistic Cu(II)/Cu(I)-mediated alkyne coupling was performed to reveal the detailed mechanism for C-C bond formation, which proceeded via an unusual dinuclear 1,2-reductive elimination. Because the reactant for dinuclear 1,2-reductive elimination was calculated to be triplet while the products were singlet, the minimum energy crossing point (MECP) was introduced to the Cu/TMEDA/alkyne system to clarify the spin crossing between triplet state and singlet state potential energy surfaces. Computational results suggest that C-H bond cleavage solely catalyzed by the Cu(I) cation is the rate-determining step of this reaction and Cu(II)-mediated dinuclear 1,2-reductive elimination after the MECP is a facile process. These conclusions are in good agreement with our previous experimental results.
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, People's Republic of China.
authors.forename: Xiaotian
authors.initials: X
authors.lastname: Qi
authors.affiliation: College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, Hubei, People's Republic of China.
authors.forename: Ruopeng
authors.initials: R
authors.lastname: Bai
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, People's Republic of China.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhu
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, People's Republic of China.
authors.forename: Rui
authors.initials: R
authors.lastname: Jin
authors.affiliation: College of Chemistry and Molecular Sciences, Wuhan University , Wuhan 430072, Hubei, People's Republic of China.
authors.forename: Aiwen
authors.initials: A
authors.lastname: Lei
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, People's Republic of China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan