title: Cobalt-catalyzed cyclotrimerization of alkynes: the answer to the puzzle of parallel reaction pathways.
abstract: To understand some experimental data at odds with the computed mechanism of the CpCo(L2)-catalyzed [2 + 2 + 2] cyclotrimerization of ethyne, DFT computations were carried out following the fate of methyl- and hydroxycarbonyl-substituted alkynes to give the corresponding arenes. The key intermediate in all cases is a triplet cobaltacyclopentadiene obtained by oxidative coupling of the corresponding CpCo(bisalkyne) complex and subsequent spin change via a minimum energy crossing point (MECP). From that species, two different catalytic cycles lead to an arene product, depending on the nature of the alkyne and other ligands present: either alkyne ligation to furnish a cobaltacyclopentadiene(alkyne) intermediate or trapping by a sigma-donor ligand to generate a coordinatively saturated cobaltacyclopentadiene(PR3) complex. The former leads to the CpCo-complexed arene product via intramolecular cobalt-assisted [4 + 2] cycloaddition, whereas the latter may, in the case of a reactive dienophile (butynedioic acid), undergo direct intermolecular [4 + 2] cycloaddition to generate a cobaltanorbornene. The bridgehead cobalt atom is then reductively eliminated after another change in spin state from singlet to triplet. The necessary conditions for one or the other mechanistic pathway are elaborated.
authors.affiliation: Université Pierre et Marie Curie-Paris 6, Laboratoire de Chimie Organique (UMR CNRS 7611), Institut de Chimie Moléculaire (FR 2769), case. 229, 4 place Jussieu, F-75252 Paris cedex 05, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Agenet
authors.forename: Vincent
authors.initials: V
authors.lastname: Gandon
authors.forename: K Peter C
authors.initials: KP
authors.lastname: Vollhardt
authors.forename: Max
authors.initials: M
authors.lastname: Malacria
authors.forename: Corinne
authors.initials: C
authors.lastname: Aubert