Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 786, Issue -, Pages 31-39Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2015.03.025
Keywords
[2+2+2] cycloaddition; Dimerization; Alkylidene ruthenium catalyst; Phenylacetylene; DFT calculation
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Funding
- PL-Grid Infrastructure
- Academic Computer Centre CYFRONET AGH [MNiSW/IBM_BC_HS21/PK/003/2013]
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Phosphine-free ruthenium alkylidene complexes, [RuCl2(=CH-o-(OPrC6H4)-Pr-i)(IMesH(2))], [Ru(CF3CO2)(2)(=CH-o-(OPrC6H4)-Pr-i)(IMesH(2))], and [RuCl2(=CHPh)(3-Br-py)(2)(IMesH(2))], were found as catalyst precursors for non-metathesis transformations of phenylacetylene, e.g. cyclotrimerization and dimerization. Selective product formation was affected by modulating the coordination sphere of the catalyst and temperature. An NMR study under various experimental conditions and DFT calculations taken together permitted the conclusion that the degradation of the alkylidene complex took place in the initial step, regardless of the manner of alkyne addition. (C) 2015 Elsevier B.V. All rights reserved.
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