Mechanistic study of acetylene carbonylation to anhydrides of dicarboxylic acids in solutions of palladium complexes

✍ Scribed by L.G. Bruk; I.V. Oshanina; A.P. Kozlova; E.V. Vorontsov; O.N. Temkin

• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 650 KB
• Volume: 104
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/1381-1169(96)00108-2

✦ Synopsis

The mechanism of the reaction that produces maleic and succinic anhydrides from carbon monoxide and acetylene was studied in the catalytic PdBr,-LiBr-CH,CN system. The in situ study of reactivities of possible organic intermediates, the kinetic isotope effect study (for succinic and maleic anhydrides kHlkD was estimated to be 1.05 k 0.05 and 0.9 f 0.1, respectively), the study of isotope exchange, and the oxygen effect on the process direction, revealed that maleic anhydride is most likely a key intermediate of the succinic anhydride formation. Maleic anhydride undergoes transformations through the mediation of a palladium hydride complex. This complex was detected in the catalytic solution at -40°C with 'H NMR (S = -1 .gg ppm, v,, 2=70Hz).