Density functional theory studies of the mechanistic aspects of olefin metathesis reactions

Dalton Transactions : an International Journal of Inorganic Chemistry
Richard Tia, Evans Adei

Abstract

The potential energy surfaces of the reactions of Cl(4)MCH(2) (M = Cr, Mo, W, Ru, Re) with ethylene, models of potential chain-carrying catalysts and olefins respectively in the transition metal-catalyzed olefin metathesis reaction, have been explored using density functional theory at the B3LYP/LACVP* level of theory. In Cl(4)MCH(2) (M = Cr, Ru), the carbenoid complexes Cl(3)MCH(2)-Cl have been found to be more stable than the corresponding carbene Cl(4)M[double bond, length as m-dash]CH(2) complexes whereas in Cl(4)MCH(2) (M = Mo, W, Re) the carbene complexes are more stable than the carbenoid complexes. The carbenoid complexes have been found not to favor the formation of metallacyclobutanes, a key step in the olefin metathesis reaction according to the Herrison-Chauvin mechanism, indicating that the active species for the metathesis reaction is a carbene complex and not a carbenoid complex. Therefore, even though the formation of metallacyclobutanes through formal [2+2] cycloaddition has been found to be a low-barrier process with each of the metal carbene complexes investigated, metathesis is likely to occur only in Cl(4)MCH(2)(M = Mo, W, Re) but not in Cl(4)MCH(2)(M = Cr, Ru) since the reaction surface in the latter compl...Continue Reading

References

Feb 15, 2001·Accounts of Chemical Research·T M Trnka, R H Grubbs
Jul 26, 2002·Journal of the American Chemical Society·Luigi Cavallo
Jun 15, 2007·Journal of the American Chemical Society·Albert PoaterOdile Eisenstein
May 1, 2008·The Journal of Physical Chemistry. a·Dilek YükselFatma Sevin

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Citations

Oct 23, 2012·Computational & Theoretical Chemistry·Dustin Wayne DemoinCarol A Deakyne
Nov 18, 2015·Journal of Chemical Theory and Computation·Lianrui Hu, Hui Chen
Oct 8, 2021·Journal of the American Chemical Society·Ushnish MandalAdam S Veige

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