From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis
作者:Sylvie Derien、Elisabet Dunach、Jacques Perichon
DOI:10.1021/ja00022a037
日期:1991.10
The incorporation of carbon dioxide into nonactivated alkynes catalyzed by electrogenerated nickel-bipyridine complexes affords alpha,beta-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacycle by magnesium ions is the key step to explain catalysis.