Manganese(II) Bromide Coordination toward the Target Product and By-Product of the Condensation Reaction between 2-Picolylamine and Acenaphthenequinone
Round 1
Reviewer 1 Report
Dear Authors,
This short communication presents the crystal structure of binuclear manganese complex. Compound was characterized by single-crystal X-ray diffraction. The experiments have been correctly analyzed. The reviewer has the following comments:
I recommend using the abbreviation ‘BIAN’ instead of ‘bian’.
It is recommended that the introduction section be revised. As far as I am concerned, the Authors should in the Introduction provide more details about the practical applications of various BIANs and their metal complexes, especially manganese.
Line 43 Given the chemical name of the ligand 2 (L2) ‘14-(pyridin-2-yl)-14H-acenaphtho[1,2-b]naphtho[1,8-fg]quinoxalin-14-ol’ should be ‘14-(pyridin-2-yl)-14H-acenaphtho[1,2-b]naphtho[1,8-fg]quinoxalin-14-ol’.
Line 23 ‘by-products shown in Scheme 1’ should be ‘by-products as shown in Scheme 1’
Line 40 ‘We manage’ should be ‘We managed’
Line 33 ‘forming’ should be ‘formed’
Line 37 ‘give a manganese complex 1’ should be ‘give manganese complex 1’
Line 37 ‘The complex 1 demonstrates’ should be ‘Complex 1 demonstrates’
Line 91 ‘Nonhydrogen atoms’ should be ‘Non-hydrogen atoms’
A Conclusion should be added. It would be helpful if Authors could provide any potential applications for the synthesized manganese complex in this work.
Author Response
Dear Reviewer,
Thank you for your fruitful revision. We have prepared a point-by-point response to the comments with all changes to the manuscript marked yellow.
Point 1. I recommend using the abbreviation ‘BIAN’ instead of ‘bian’.
Response 1. We have changed “bian” to “BIAN”.
Point 2. It is recommended that the introduction section be revised. As far as I am concerned, the Authors should in the Introduction provide more details about the practical applications of various BIANs and their metal complexes, especially manganese.
Response 2. We have improved the Introduction section by adding text about the practical applications of various BIANs and their metal complexes, especially manganese ones.
Point 3.
Line 43 Given the chemical name of the ligand 2 (L2) ‘14-(pyridin-2-yl)-14H-acenaphtho[1,2-b]naphtho[1,8-fg]quinoxalin-14-ol’ should be ‘14-(pyridin-2-yl)-14H-acenaphtho[1,2-b]naphtho[1,8-fg]quinoxalin-14-ol’.
Line 23 ‘by-products shown in Scheme 1’ should be ‘by-products as shown in Scheme 1’
Line 40 ‘We manage’ should be ‘We managed’
Line 33 ‘forming’ should be ‘formed’
Line 37 ‘give a manganese complex 1’ should be ‘give manganese complex 1’
Line 37 ‘The complex 1 demonstrates’ should be ‘Complex 1 demonstrates’
Line 91 ‘Nonhydrogen atoms’ should be ‘Non-hydrogen atoms’
Response 3.
All mistakes and shortcomings have been checked and corrected.
Point 4. A Conclusion should be added. It would be helpful if Authors could provide any potential applications for the synthesized manganese complex in this work.
Response 4. The conclusion section has been added at the end.
Thank you.
Yours sincerely,
Authors
Reviewer 2 Report
This manuscript describes the product in the reaction of 2-picolyl amine and acenaphtequinone with Na and MgBr2. The structure of the product is unique. Therefore, I think this manuscript is acceptable as a Communication in Molbank. However, I hope to add the plausible reaction mechanism on generation of complex 1, if possible.
Author Response
Dear Reviewer,
Thank you for your fruitful revision. We have prepared a point-by-point response to the comments with all changes to the manuscript marked yellow.
Point 1. This manuscript describes the product in the reaction of 2-picolyl amine and acenaphtequinone with Na and MgBr2. The structure of the product is unique. Therefore, I think this manuscript is acceptable as a Communication in Molbank. However, I hope to add the plausible reaction mechanism on generation of complex 1, if possible.
Response 1. We have provided Scheme 2 in Text. As was described in Introduction, when a primary alkyl- amine interacts with acenaphthenequinone, several side reactions can occur simultaneously or sequentially; therefore, as a rule, side products of the reaction predominate in the reaction mixture. In our case, the reaction mechanism is probably the sum of the described reactions of isomerization, hydrolysis, and tautomerization and cannot be presented.
Thank you.
Yours sincerely,
Authors
Reviewer 3 Report
Although the present work is not of great interest for the community and will have no impact, it fits with the Special Issue "Molecules from Side Reactions II".
Before acceptance, could the authors explain why the used metallic sodium? And the role of MnBr2 ? It seems that they targeted the MnBr2 complex of the mono-iminoacenaphthene ligand ? Why did they do not try to react both 2-aminomethyl-pyridine and acenaphtenequinone directly in the presence of MnBr2 (template effect as described in Organometallics 2002, 21, 14, 2950–2957)?
Could the authors:
* provide a Conclusion and Perspectives.
* check the meaning and correct "All manipulations were carried out in a vacuum or under nitrogen ..." (??)
* add this ref (Organometallics 2002, 21, 14, 2950–2957) and explain the template effect for BIAN synthesis
If these points are addressed, the paper may be accepted in Molbank
Author Response
Dear Reviewer,
Thank you for your fruitful revision. We have prepared a point-by-point response to the comments with all changes to the manuscript marked yellow.
Point 1. Before acceptance, could the authors explain why the used metallic sodium? And the role of MnBr2 ? It seems that they targeted the MnBr2 complex of the mono-iminoacenaphthene ligand ?
Response 1. Based on NMR data, the reaction mixture obtained was not identifiable and was air sensitive. Due to the potential redox activity of the target product and in order to isolate the one-electron reduction product, sodium was added. After the sodium reacted and recrystallization did not help, we added manganese bromide to isolate at least some reaction product and characterize it.
Point 2. Why did they do not try to react both 2-aminomethyl-pyridine and acenaphtenequinone directly in the presence of MnBr2 (template effect as described in Organometallics 2002, 21, 14, 2950–2957)?
Response 2. Several synthetic approaches to obtaining bians or mians are possible, namely, the template synthesis of bians based on insoluble Zn(II), Ni(II), Mn(II) salts or the transimination reaction based on the replacement of EW (electron-withdrawing) by the substituent ED (electron-donating) [DOI: 10.1038/s42004-020-00359-0]. Another way to obtain bians is a direct reaction between acenaphthenquinone and a primary amine. For example, for the synthesis of Cypr-BIAN, the presence of ZnCl2 is not required. [DOI: 10.1039/B415767B].
Point 3. Could the authors:
* provide a Conclusion and Perspectives.
Response 3. We added the Conclusion section to the article.
Point 4. * check the meaning and correct "All manipulations were carried out in a vacuum or under nitrogen ..." (??)
Response 4. Corrected
Point 5. * add this ref (Organometallics 2002, 21, 14, 2950–2957) and explain the template effect for BIAN synthesis
Response 5. We added ref (Organometallics 2002, 21, 14, 2950–2957).
Thank you.
Yours sincerely,
Authors
