Assessment of density functional methods for the study of olefin metathesis catalysed by ruthenium alkylidene complexes

作者：Sliwa Pawel; Handzlik Jaroslaw^*

来源：Chemical Physics Letters, 2010, 493(4-6): 273-278.

DOI：10.1016/j.cplett.2010.05.066

Performance of 31 DFT methods in thermochemistry of olefin metathesis involving the model catalyst (PH3)(2)(Cl)(2)Ru=CH2 is studied using the CCSD(T) reference energies. The best methods are M06, omega B97X-D and PBE0, followed by MPW1B95, LC-omega PBE, M05-2X and B1B95. Among 20 functionals tested in reproduction of experimental PCy3 dissociation energy for the Grubbs catalyst (H(2)IMes)(PCy3)(Cl)(2)Ru=CHPh, the M06-class and M05-2X methods are most accurate. omega B97X-D overestimates the dissociation energy, whereas MPW1B95, LC-omega PBE, PBE0 and B1B95 underestimate it, similarly to other methods, which give larger errors. LC-omega PBE, B1B95, MPW1B95 and PBE0 provide the best geometries.

• 出版日期2010-6-25