Evidence for a Carbon−Carbon Coupling Reaction To Proceed through a Planar-Tetracoordinate Carbon Intermediate

Evidence for a Carbon−Carbon Coupling Reaction To Proceed through a Planar-Tetracoordinate Carbon Intermediate

Treatment of bis(propynyl)zirconocene with B(C6F5)3 results in a linear C−C coupling of the alkynyl ligands to form the zwitterionic complex 3. Its treatment with excess RC⋮N yields an organometallic methylenecyclopropene derivative (6). This reaction topologically requires a very endothermic substi...

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Veröffentlicht in:Organometallics 2004-09, Vol.23 (19), p.4391-4395
Hauptverfasser: Erker, Gerhard, Venne-Dunker, Sabine, Kehr, Gerald, Kleigrewe, Nina, Fröhlich, Roland, Mück-Lichtenfeld, Christian, Grimme, Stefan
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container_end_page 4395
container_issue 19
container_start_page 4391
container_title Organometallics
container_volume 23
creator Erker, Gerhard
Venne-Dunker, Sabine
Kehr, Gerald
Kleigrewe, Nina
Fröhlich, Roland
Mück-Lichtenfeld, Christian
Grimme, Stefan
description Treatment of bis(propynyl)zirconocene with B(C6F5)3 results in a linear C−C coupling of the alkynyl ligands to form the zwitterionic complex 3. Its treatment with excess RC⋮N yields an organometallic methylenecyclopropene derivative (6). This reaction topologically requires a very endothermic substituted butenyne to methylenecyclopropene cyclization to become energetically feasible by suitable stabilization effects. A DFT study has revealed that the 3 → 6 conversion is probably triggered by nitrile addition to the metal with formation of a planar-tetracoordinate carbon intermediate, featuring coordination of the three-membered carbocycle through one of its carbon−carbon σ bonds.
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title Evidence for a Carbon−Carbon Coupling Reaction To Proceed through a Planar-Tetracoordinate Carbon Intermediate
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