期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 682, 期 1-2, 页码 204-211出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(03)00783-6
关键词
ruthenium; alkynes; cyclotrimerization; arene complexes; DFT calculations
The substitutionally labile cationic complex [RuCp(CH3CN)(3)](+) (as the PF6- salt) was tested with respect to its ability to catalyze the cyclotrimerization of terminal alkynes and diynes to afford benzene derivatives. Whereas [RuCp(CH3CN)(3)](+) is in fact promoting the catalytic cyclotrimerization of alkynes, the formation of stable and inert sandwich complexes of the type [RuCp(eta(6)- arene)](+) deactivates the catalyst and thus quenches the catalytic cycle. All new sandwich complexes were isolated and characterized spectroscopically. A proposal for a plausible catalytic cycle including possible degradation pathways of the catalyst is presented based on DFT calculations. As key intermediates several novel carbene complexes have been identified including metallacyclo-pentatriene and metallaheptatetraene species. (C) 2003 Elsevier B.V. All rights reserved.
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