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Density Functional Theory Mechanistic Study of Ni-Catalyzed Reductive Alkyne-Alkyne Cyclodimerization: Oxidative
Xiaojian Ren1, Yu Lu1, Gang Lu2
1School of Chemical Sciences, University of the Chinese Academy of Sciences, Beijing 100049, China.
Abstract:
Density functional theory mechanistic study of the nickel-catalyzed reductive alkyne-alkyne cyclodimerization with CH3OH/BEt3 unveils that, after forming a nickel-alkyne π complex, the reaction prefers outer-sphere proton transfer rather than the common alkyne-alkyne oxidative cyclization. The outperformance of aminophosphine ligand (L1) is attributed to its bidentate coordination that favors the proton transfer, the labile -NH2 and strong electron-donating -PPh2 arms and adequate Ni-P distance that allow the hydrogen transfer of the ethyl group of MeO-BEt3-.
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