Content of review 1, reviewed on November 28, 2023

The authors detailed the investigation of acid-catalyzed oxime metathesis reactions between a wide substrate scope of aryl oximes with electron withdrawing, donating, or neutral groups para to the oxime. They proposed a mechanism of acid-catalyzed oxime metathesis and performed computational studies to compare the metathesis energetics with and without acid catalyst present, showing the necessity of the catalyst in lowering the transition state energies that allow the reactions to proceed. Further computations were done to compare EDG/EWG/Neutral aryl oxime pairs to elucidate how the substituent groups on the aryl ring affect the activation energies of metatheses between different oxime pairs that were corroborated experimentally. Furthermore, to exhibit this system’s utility, they made covalent adaptable networks (vitrimers) with di/trithiols and allyl dioximes, that function based on the oxime metathesis providing dynamic crosslinks in the system in conjunction with the permanent thiol-ene crosslinks.

The research presented here, to the best of my knowledge, is novel and constitute important findings in oxime chemistry and CAN polymer science. The robust oxime (compared to imine) bonds have been shown here to provide much more stable network constituents, providing a durable platform for further CAN development. The studies conducted, both experimental and computational, were detailed and useful for explaining the phenomena observed. Figure 1 could benefit from restructuring for clarity, and including figures S1, S2, and table S1 in the main text would benefit the main text greatly. Furthermore, questions raised above should be addressed to improve the reasoning of the authors’ choices and observations. Overall, the chemistry here seems really well-fleshed out and could have significant impact on future CAN development. However, the grammar of the text has much to be desired of and can make certain parts of the text confusing to read. I suggest the paper be published with minor revisions, showing explicit detail in overarching improvements to the text’s grammar and sentence structure. Again, the comments raised above should also be addressed.

Figure 1:
• The caption could use some more explanation for clarity. Label which specific reactions are the imine metathesis, transimination, and imine formation/hydrolysis.
• The combined schemes in the “previous works” part could also be spaced out, they’re crammed together which makes it a little difficult to decipher.
• What specifically is the blue box to the right of the arrow referring to? Fast kinetics and versatility of what?
Page 2, paragraphs 2:
• Why select these specific acids/bases and why use four of them? Why didn’t the bases work?
Page 2, paragraph 3:
• When the reaction reached equilibrium, was there a 50/50 distribution of metathesized products and remaining reactants since the computations suggest isoergonic transitions from INT back to reactants and forward to products? If not, what was the driving force behind the reaction favoring one side or the other?
• The paper would greatly benefit from having Figures S1, S2, and Table S1 in the main text. Since Chem Com EDGE articles have no page limit, I don’t see why they’ve been relegated to the SI.
Page 4, paragraph 1
• Since the FT-IR didn’t work at all, how was thiol-ene formation quantified?
Page 4, paragraph 3
• If FTIR didn’t work for initial vitrimer characterization, why did it work after reprocessing? Perhaps a small molecule study could be conducted similar to the initial substrate scope to model the network formation that could be quantified by 1H-NMR or a similar method.

The manuscript is in need of very thorough proofreading and editing.

Source

    © 2023 the Reviewer.

References

    Luca, P., Marta, X., Francesca, L., Giulia, V., Enrico, B., Fermin, E., Haritz, S. 2024. Oxime metathesis: tuneable and versatile chemistry for dynamic networks. Chemical Science.