title: Computational characterization of the mechanism for coinage-metal-catalyzed carboxylation of terminal alkynes.
abstract: Several experimentally reported copper-, silver-, and gold-catalyzed carboxylation processes of terminal alkynes are studied with DFT methods to find out the mechanism ruling these transformations. The computational results indicate that the reaction follows a very similar pathway for all three metals: the crucial step involves the electrophilic attack of an unactivated carbon dioxide unit on a metal-σ-acetylide complex. The calculations lead to the proposal of additional silver and gold catalytic systems that could perform this reaction at mild temperatures.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ) , Avgda. Països Catalans 16, 43007 Tarragona, Catalonia, Spain.
authors.forename: Jesús
authors.initials: J
authors.lastname: Jover
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras