Acetylene catalytic hydrochlorination over mechanically pre-activated K2PdCl4 salt: A study of the reaction mechanism

作者：Krasnyakova Tatyana V; Zhikharev Igor V; Mitchenko Regina S; Burkhovetski Valeriy I; Korduban Alexander M; Kryshchuk Taras V; Mitchenko Serge A^*

来源：Journal of Catalysis, 2012, 288: 33-43.

DOI：10.1016/j.jcat.2011.12.020

• Mechanical activation
• Heterogeneous catalysts
• Active sites
• Acetylene
• Hydrochlorination
• Reaction mechanism

Mechanical pre-grinding of solid K2PdCl4 in a vibratory micromill under acetylene or propylene atmosphere leads to the formation of catalyst for acetylene hydrochlorination by gaseous HCl. The active sites of the heterogeneous catalyst are Pd(II)chloro complexes with a coordination vacancy, capable reversibly form pi-acetylene complexes. The HCl molecules participate in two steps of the reaction: acetylene chloropalladation (rate-limiting step) forming intermediate sigma-chlorovinyl Pd(II) derivative and protonolysis of the last one.

• 出版日期2012-4