Towards Construction of the “Periodic Table” of 1-Methylbenzotriazole

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

This review summarises practically all coordination chemistry of 1-methylbenzotriazole, including a number of examples by the authors themselves. Even if the manuscript contains plenty of self-citations, the citations are justified. In general, the manuscript is well-written and even quite amusing to be read. There are just a few minor pointsto be considered prior to the publication.

- Are these ligands redox non-innocent? Irf so, that coud be mentioned.

- Some "Figures" are actually Charts (e.g. Figure 1) or Schemes (e.g. Figure 2), but I am not sure if Inorganics accept the present format.

- Line 173, "Orthohydroxyphenyl benzotriazoles 173 (Figure 5) are among the best ultraviolent absorbers...". Should be Figure 4, I think.

 

Author Response

“- Are these ligands redox non-innocent? If so, that could be mentioned”

Benzotriazoles are redox “innocent”. We have added this information in the last paragraph of section 3 (second sentence).

“- Some "Figures" are actually Charts (e.g. Figure 1) or Schemes (e.g. Figure 2), but I am not sure if Inorganics accept the present format.”

The comment is correct. However, we checked several articles of INORGANICS and we realized that the journal generally accepts the format that we have used in the present Review.

“- Line 173, "Orthohydroxyphenyl benzotriazoles 173 (Figure 5) are among the best ultraviolent absorbers...". Should be Figure 4, I think.”

This comment is correct. We had not incorporated a figure illustrating the structural formula of orthophenyl benzotriazoles in the original manuscript, since this is obvious even for an undergraduate student. Thus, we have deleted “(Figure 5)” from section 3. Figure 4 does not refer to ultraviolet absorbers, but instead to benzotriazole derivatives which are efficient energetic compounds.

We are grateful to Reviewer 1 for her/his time to study our ms and for the valuable revision points/comments/suggestions. 

Reviewer 2 Report

Comments and Suggestions for Authors

Chasapis, Perlepes and coworker summarized the recent progress on the preparation and characterization of 1-methylbenzotriazole (Metba)-ligated inorganic metal complexes including a variety of transitional metals such as Mn(II), fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), Zn(II) and Au(I), etc. The review was well-organized, well-written and easy to understand. I suggest to accept it after minor revision.

P35， Silver(II) should be Silver (I)

Author Response

“P35, Silver(II) should be Silver (I)”

It was our mistake and it has been corrected to “Silver(I)” in the revised ms.

We are grateful to Reviewer 2 for her/his time to study our ms and for the valuable revision point. 

Reviewer 3 Report

Comments and Suggestions for Authors

Present review focuses on the comprehensive evaluation of the coordinative potential of the 1-methylbenzotriazole ligand. And I do mean that it is a  comprehensive piece of work, that deserves its title of the 'periodic table'.

Authors rightfully justify the need for this work and do not overstate things. It will be particuarly interesting for coordination chemists and people that deal with the crystal engineering aspects. Although the benzotriazole system was well-studied and is not that complicated, there is a need for thorough works like this, which gathers all the data found in the literature and compares those. Especially that there is a bunch of unpublished data by the authors, which are also adequately referred herein.

I believe the work can be published as is, provided the following is added (either in the form of discussion or a few extra sencences)

- additional insight about the s- and f-blocks coordination chemistry of triazoles would be a nice addition (here, the d-block is the main focus, plus examples from the p-block - I think that there aren't many compounds from other groups, but it would be relevant to comment on them at least in a separate paragraph)

- very often differences arise from the solid state/solution state behaviour of the coordination compounds. Here, NMR and other related techniques were noted for a few examples where solid state characterization could not be performed, but it would be good to let the readers know what is the solution behaviour of benzotriazole-based systems. Are they stable? Is the solid state also represented in solution?

- a table of contents would be a good addition here as well

Author Response

“- additional insight about the s- and f-blocks coordination chemistry of triazoles would be a nice addition (here, the d-block is the main focus, plus examples from the p-block - I think that there aren't many compounds from other groups, but it would be relevant to comment on them at least in a separate paragraph)”

The comment is absolutely correct. We have added the required information in three parts of the revised ms. First, in the last paragraph of section 3 (“Perusal of references [46-74]……f-block metal ions”) which refers generally to the benzotriazoles as ligands in inorganic chemistry. Second, in the first paragraph of section 7 where we briefly commented on the so far known coordination chemistry of Mebta (“We can easily see……….metal starting materials”). And third, in the last paragraph of section 7 which refers to the published coordination chemistry of the similar, less bulky ligand 1-methyl-1,2,3-triazole (Meta). Thus, the reader can obtain a general knowledge about the metal complexes of benzotriazoles, and a more specific knowledge about the to-date known coordination chemistry of Mebta and Meta, all three in relation to the Periodic Table of the Elements (s-, p-, d- and f-block metal ions).

“- very often differences arise from the solid state/solution state behaviour of the coordination compounds. Here, NMR and other related techniques were noted for a few examples where solid state characterization could not be performed, but it would be good to let the readers know what is the solution behaviour of benzotriazole-based systems. Are they stable? Is the solid state also represented in solution?”

This comment is also correct and valuable. We have added a new, detailed paragraph in section 7 (“Concluding Remarks in Brief and Prognosis for the Future”), where we discuss in detail (based on NMR spectroscopy and molar conductivity experiments) the differences between the solid-state and solution coordination chemistry of Mebta. Two new chemical equations, Equations (29) and (30), have been added in the revised section 7 to make clear what is described in the text. Thus, now the readers know what is the solution behavior of Mebta-based metal complexes.

“- a table of contents would be a good addition here as well”

This suggestion appears valuable for the readers. Following the advice by the reviewer, we have “created” a “Table of Content” part, which has been placed before the beginning of the main ms, i.e. just before section 1 (“Introduction”).

We are grateful to Reviewer 3 for her/his time to study our ms and for the valuable revision points/comments/suggestions.