Catalytic Carbon−Carbon and Carbon−Silicon Bond Activation and Functionalization by Nickel Complexes
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 comp...
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Published in | Organometallics Vol. 18; no. 22; pp. 4660 - 4668 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
25.10.1999
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | 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. |
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Bibliography: | ark:/67375/TPS-XNFX69B0-V istex:7A172BE3927BC93AD109189C4693DF46126D233A USDOE FG02-86ER13569 |
ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om990457l |