title: Phosphine-alkene ligands as mechanistic probes in the Pauson-Khand reaction.
abstract: An alkyne tetracarbonyl dicobalt complex with a chelated phosphine-alkene ligand, in which the phosphorus atom and the alkene from the ligand are attached to the same cobalt atom has been prepared, isolated, and characterized by X-ray crystallography. The complex serves as a mechanistic model for an intermediate of the Pauson-Khand (PK) reaction. Although the alkene fragment is located in an equatorial coordination site with an appropriate orientation, and, therefore, should undergo insertion, it failed to give the PK product upon either thermal or N-methylmorpholine N-oxide activation. However, a phosphine-alkene complex that contains a terminal alkene readily provided the corresponding PK product. We attribute this change in reactivity to the different ability of each olefin to undergo 1,2-insertion. These results provide further insights into the factors that govern a crucial step in the PK reaction, the olefin insertion.
authors.affiliation: Unitat de Recerca en Síntesi Asimètrica (URSA)-PCB, Institute for Research in Biomedicine (IRB) Barcelona and Departament de Química Orgànica, Universitat de Barcelona, c/Baldiri Reixac 10, 08028 Barcelona, Spain.
authors.forename: Catalina
authors.initials: C
authors.lastname: Ferrer
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.forename: Antoni
authors.initials: A
authors.lastname: Riera
authors.forename: Xavier
authors.initials: X
authors.lastname: Verdaguer
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D000480:Alkynes; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D003035:Cobalt; C044646:phosphine