On 2016 Feb 03, Pedro Silva commented:

I am glad that Kosak et al. were able to improve the description of this reaction mechanism, and to find a superior pathway vs. the bimolecular mechanism I proposed with Carla Sousa (http://dx.doi.org/10.1002/ejoc.201300337 , with erratum at http://dx.doi.org/10.1002/ejoc.201301647).

The following text would be most relevant in an entry for http://dx.doi.org/10.1002/ejoc.201300337, which is unfortunately unavailable in PubMed. It may nonetheless be useful for readers of the present paper.

Upon reading this paper, I realized that I had not been completely clear regarding the reaction barrier of the bimolecular pathway. Our computations of that barrier were performed as:

Gº(TS) -Gº(anisole:anisole prereaction complex )

rather than :

Gº(TS) - 2* Gº(anisole)

The barrier we depicted did not therefore include the translational entropy component of ca. 10 kcal.mol-1 . We performed the computation in that way because the computation of entropy changes upon binding in solution (reviewed by Zhou and Gilson, Chem.Rev. 2009,109,4092-4107 DOI: 10.1021/cr800551w) is still somewhat contentious, and can be argued to depend on the relative magnitude of the volume of the complex vs. the expected volume available to a molecule in solution at a standard concentration of 1 mol.L-1 (1661 cubic angstrom). I feared that including the entropy values "as provided" by the program in gas phase would unreasonably inflate that estimate, especially because of the relatively large dimensions of the anisole:anisole complex (vs. the "theoretical cubic cage" of length 11.8 angstrom and 1661 angstrom3 volume).

In case any readers find it useful for additional investigations, I have placed all my results (ca. 11 GB) in figshare.

http://figshare.com/articles/Supporting_info_for_DOI_10_1002_ejoc_201300337/1541140

On 2016 Feb 03, Pedro Silva commented:

I am glad that Kosak et al. were able to improve the description of this reaction mechanism, and to find a superior pathway vs. the bimolecular mechanism I proposed with Carla Sousa (http://dx.doi.org/10.1002/ejoc.201300337 , with erratum at http://dx.doi.org/10.1002/ejoc.201301647).

The following text would be most relevant in an entry for http://dx.doi.org/10.1002/ejoc.201300337, which is unfortunately unavailable in PubMed. It may nonetheless be useful for readers of the present paper.

Upon reading this paper, I realized that I had not been completely clear regarding the reaction barrier of the bimolecular pathway. Our computations of that barrier were performed as:

Gº(TS) -Gº(anisole:anisole prereaction complex )

rather than :

Gº(TS) - 2* Gº(anisole)

The barrier we depicted did not therefore include the translational entropy component of ca. 10 kcal.mol-1 . We performed the computation in that way because the computation of entropy changes upon binding in solution (reviewed by Zhou and Gilson, Chem.Rev. 2009,109,4092-4107 DOI: 10.1021/cr800551w) is still somewhat contentious, and can be argued to depend on the relative magnitude of the volume of the complex vs. the expected volume available to a molecule in solution at a standard concentration of 1 mol.L-1 (1661 cubic angstrom). I feared that including the entropy values "as provided" by the program in gas phase would unreasonably inflate that estimate, especially because of the relatively large dimensions of the anisole:anisole complex (vs. the "theoretical cubic cage" of length 11.8 angstrom and 1661 angstrom3 volume).

In case any readers find it useful for additional investigations, I have placed all my results (ca. 11 GB) in figshare.

http://figshare.com/articles/Supporting_info_for_DOI_10_1002_ejoc_201300337/1541140