RT Journal Article
T1 DFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations
A1 Cambeiro Cambeiro, Fermín
A1 Martínez Núñez, Emilio
A1 Varela Carrete, Jesús Ángel
A1 Saá Rodríguez, Carlos
K1 Density functional calculations
K1 Energetic spam model
K1 Kinetic Monte Carlo simulations
K1 Ruthenium vinyl carbenes
K1 TOF
AB Mechanistic pathways for the cyclization of 1,5-alkynylacetal with N2CHTMS in the presence of Cp- and Cp*RuCl(cod) to afford Z and E (trimethylsilyl)vinyl spiroacetals have been calculated. Calculations show the presence of three conformers in equilibrium for the initially formed ruthenium carbenes. Differences in the stabilities and reactivities of the conformers, depending on the use of a Cp- or Cp*-ruthenium catalyst, are responsible for the favorable active reaction pathways in each case, even though the geometry of the resulting product is the same regardless of the catalyst used. Kinetic Monte Carlo (KMC) simulations with rate coefficients, including tunneling probabilities for the hydride transfer step, were used to model the evolution of reactants, intermediates and products for all calculated pathways. It was shown that one path is almost exclusively active for each catalyst. Finally, the energetic span model of Kozuch and Shaik was used to calculate the energetic span (δE), the TOF-determining transition state (TDTS), the TOF-determining intermediate (TDI) and the TOF value for each of the feasible mechanistic pathways.
PB American Chemical Society
YR 2015
FD 2015
LK http://hdl.handle.net/10347/23349
UL http://hdl.handle.net/10347/23349
LA eng
NO Cambeiro, F., Martínez-Núñez, E., Varela, J. A., Saá, C. (2015). DFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations. ACS Catalysis, 5, 11, 6255-6262
NO NOTICE: This is the peer reviewed version of the following article: Cambeiro, F., Martínez-Núñez, E., Varela, J. A., Saá, C. (2015). DFT and Kinetic Monte Carlo Study of TMS-Substituted Ruthenium Vinyl Carbenes: Key Intermediates for Stereoselective Cyclizations. ACS Catalysis, 5, 11, 6255-6262. [doi: 10.1021/acscatal.5b01333]. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archiving
NO This work was supported by MICINN (Spain) (projects CTQ2011-28258 and CTQ2014-51912REDC), Xunta de Galicia, and the Euro-pean Regional Development Fund (projects GRC2014/032 and EM 2012/051). F.C. thanks XUGA for a predoctoral contract
DS Minerva
RD 3 may 2026