| Popis: |
The gold-catalyzed hydration of 2-phenyl- or 2,2-diphenylcyclopropyl acetylene, sensitive probes to trace the formation of vinyl carbocations, provides exclusively the corresponding cyclopropyl methyl ketones. On the other hand, in the Ag(I)- or Fe(III)-catalyzed hydration, a profound vinyl carbocationic character appears in the initially formed metal-alkyne complexes, as judged by the partial (Ag(+)) or exclusive (Fe(3+)) formation of allene-type rearrangement products. These findings provide clear evidence for subtle electronic differences in metal-alkyne complexes, including Au(I or III), Ag(I), Fe(III), and Hg(II). |
