Carbon-carbon bond formation by electrophilic addition at the central carbon of the mu-eta(3)-allenyl/propargyl ligand on the Pd-Pd bond

Citation
S. Ogoshi et al., Carbon-carbon bond formation by electrophilic addition at the central carbon of the mu-eta(3)-allenyl/propargyl ligand on the Pd-Pd bond, J AM CHEM S, 123(14), 2001, pp. 3223-3228
Citations number
36
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
0002-7863 → ACNP
Volume
123
Issue
14
Year of publication
2001
Pages
3223 - 3228
Database
ISI
SICI code
0002-7863(20010411)123:14<3223:CBFBEA>2.0.ZU;2-7
Abstract
The mu-eta (3)-allenyl/propargyldipalladium complexes were synthesized by t he reaction of the corresponding eta (1)-allenyl- or eta (1)-propargylpalla dium complexes with Pd-2(dba)(3) The X-ray diffraction analysis indicates t hat the dinuclear complex has a unique structure, in which two palladium, t hree carbon, two phosphorus, and one halogen atoms are in the same plane. T hese dinuclear complexes react with electrophiles, such as HCl or AcCl, at the central carbon of the mu-eta (3)-allenyl/propargyl ligand to give the m u-eta (3)-vinylcarbenedipalladium complexes. Intramolecular reaction procee ded smoothly to give cyclization products quantitatively. Addition of a cat alytic amount of a palladium(0) complex dramatically accelerated the carbon -carbon bond formation. The MO calculations on the mu-eta (3)-allenyl/propa rgyl complexes indicated that the reaction proceeds via orbital control.