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Updated: May 9, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Electrosynthesis of 1,3-butadiene from dilute acetylene over coordination-modulated dicopper molecular catalysts
Wenzhe Xu1,2, Pengfei Gao3, Jianfeng Wu1
1School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, PR China.
Abstract:
Electrosynthesis of 1,3-butadiene from acetylene offers a promising alternative to energy-intensive industrial processes. Nonetheless, achieving selective hydrodimerization of acetylene remains challenging due to competing side reactions, particularly for dilute coal-derived acetylene. Herein, we synthesize a series of dicopper paddlewheel Cu2(LCOO)4 (L = tert-butyl, isopropyl, ethyl, and methyl), featuring bidentate bridging carboxylate ligands with specific Cu···Cu distances for electrocatalytic hydrodimerization of acetylene to 1,3-butadiene. Through catalyst benchmarking, in situ spectroscopy and computational analysis, we reveal that sequential modulation of carboxylate ligands (methyl → ethyl → isopropyl → tert-butyl) progressively enriches electron density at dicopper sites while strengthening structural robustness across the Cu2(LCOO)4 series. The optimized Cu2(tert-butylCOO)4 exhibits favorable reaction energetics for acetylene dimerization and subsequent hydrogenation, achieving 91% Faradaic efficiency with a 1,3-butadiene formation rate of 0.93 mmol h-1 cm-2 in a flow cell. For simulated production of 1,3-butadiene from coal-derived acetylene (15%) in a membrane electrode assembly system, this catalyst demonstrates 83% Faradaic efficiency at -300 mA. This work highlights an effective coordination modulation strategy for producing 1,3-butadiene via dicopper molecular catalysts.
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The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...