Application Cross-Coupling with a Bidentate Pd Complex

Application Cross-Coupling with a Bidentate Pd Complex 

The calculations were carried out using B3LYP with a double- basis set including polarization and diffuse functions, in gas phase and only adding ZPE to the electronic energy. Admittedly, by today s standards this may be unpublishable, but it still contains some deep qualitative insights that we can use for pedagogical purposes. 

If we try to calculate the prospective energy spans for these systems 5E and 

TS and the intermediate, without all the previous mathematical acrobatics. Strictly speaking, we must use Gibbs enei ies for this, but sometimes the electronic enei or the enthalpy are also used (this only has physical sense if the difference between these measures is ins nificant, especially when AS is negl ible). Herein, SE will stand for the apparent activation Gibbs enei in a non-Arrhenius way. 

Several conclusions can be derived from these equations first, neither of the two catalysts will work (at least based on these calculations). Being the apparent activation energy of the reaction, a 5E higher than 25 kcal mol will not provide a good catalyst, unless under extremely severe conditions 5E = 25 kcal mol will deliver a TOE of only 1 min at 100 C). 

---