Catalytic Carbon−Carbon and Carbon−Silicon Bond Activation and Functionalization by Nickel Complexes

• Published in: Organometallics Vol. 18; no. 22; pp. 4660 - 4668
• Main Authors: Edelbach, Brian L, Lachicotte, Rene J, Jones, William D
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 25.10.1999; Amer Chemical Soc
• Subjects: 40 CHEMISTRY; ALKYNES; CHEMICAL ACTIVATION; CHEMICAL REACTION KINETICS; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; CRYSTAL STRUCTURE; HOMOGENEOUS CATALYSIS; NICKEL COMPLEXES; Physical Sciences; Science & Technology; SILANES; PALLADIUM; INSERTION; DISPROPORTIONATION; HYDROGENOLYSIS; RUTHENIUM; METAL-CLUSTERS; HYDROSILATION; RHCL(PIPR3)2; OXIDATIVE ADDITION; PHOSPHINE COMPLEXES
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om990457l

The nickel alkyne complexes (dippe)Ni(Me3SiC⋮CSiMe3), 1, (dippe)Ni(Me3CC⋮CSiMe3), 2, and (dippe)Ni(MeC⋮CSiMe3), 3, were synthesized (dippe = bis(diisopropylphosphino)ethane) and characterized by 1H, 31P, and 13C{1H} NMR spectroscopy. Complex 1 was characterized by X-ray crystallography. Heating complex 1, 2, or 3 with excess biphenylene and alkyne results in the catalytic formation of several novel organic compounds, several of which have been characterized by X-ray crystallography. These reactions are proposed to proceed by a competition between β-silyl migration from an acetylene insertion intermediate and elimination of phenanthrene. Mechanistic schemes are presented for these reactions.