1997/03/01 by Qiang Xü, Yuki Imamura, Masahiro Fujiwara +1 · 5 citations
Chemistry · Engineering · #Catalysis and Hydrodesulfurization Studies #Catalytic Alkyne Reactions #Organometallic Complex Synthesis and Catalysis
paper · doi:10.1021/jo9620122
openalex publication_date 1997/03/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/26
A new gold catalyst, [Au(CO) n ] + ( n = 1, 2), was synthesized by using a facile method from commercial gold(III) oxide, Au 2 O 3, in concentrated H 2 SO 4, which exhibits high catalytic activity for carbonylation of olefins. The gold monocarbonyl [Au(CO)] + ( 1 ) and dicarbonyl [Au(CO) 2 ] + ( 2 ) cations coexist in H 2 SO 4 solution, the former of which is much more stable than the latter. Both of the carbonyls show IR spectra of ν CO (2194, 2208 cm - 1 ) higher than that of free CO (2143 cm - 1 ), indicating nonclassical (σ-only) gold−CO bonding. The gold carbonyl complexes coexisting in the concd H 2 SO 4 solution exhibit a single resonance in the 13 C NMR spectrum at 171 ppm at ambient temperature and pressure, reflecting rapid CO exchange between 1 (164 ppm) and 2 (175 ppm). The nonclassical gold(I) carbonyl solution worked as an excellent catalyst, with which olefins reacted with CO to give tert -carboxylic acids in good yields at room temperature and atmospheric pressure. The gold(I) dicarbonyl cation 2 was found to function as an active species for the carbonylation. An olefin−gold(I)−carbonyl complex was proposed as a possible intermediate in the metal carbonyl-catalyzed carbonylation in the strongly acidic medium.