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过氧甲酸分解机理的合理化：理解溶剂影响的计算见解。

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence.

机构信息

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science & Technology (BIST), Av. Països Catalans, 16, 43007, Tarragona, Spain.

Departament de Química Física i Inorgànica, Universitat Rovira i Virgili (URV) C/ Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.

出版信息

Chemistry. 2021 Aug 11;27(45):11618-11626. doi: 10.1002/chem.202100755. Epub 2021 Jun 26.

DOI:10.1002/chem.202100755
PMID:34076322
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8457178/
Abstract

The heterolytic decomposition of tert-butyl peroxyformate to tert-butanol and carbon dioxide, catalyzed by pyridine, is a long-known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine-mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)-def2-TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.

摘要

过氧叔丁酯在吡啶催化作用下异裂生成叔丁醇和二氧化碳，这是一个众所周知的例子，其动力学强烈受到溶剂极性的影响。通过 DFT 和从头算方法以及 SMD 隐式溶剂化模型，提出了对以前接受的机制的扩展。这个新的提议涉及碳酸酯中间体的形成及其进一步分解，通过以前未报道的吡啶介导的逐步途径。在 DLPNO/CCSD(T)-def2-TZVP 水平上，该机制的计算势垒与不同溶剂中的实验动力学数据非常吻合。此外，还深入分析了活化能、过渡态的几何参数与不同溶剂特性之间的关系。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/ee00231452dd/CHEM-27-11618-g002.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/5ecdf37b7214/CHEM-27-11618-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/2757562ad33a/CHEM-27-11618-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/e6453eacb4c0/CHEM-27-11618-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/598a10a35151/CHEM-27-11618-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/6ba3b1c6f0c5/CHEM-27-11618-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/901dab2afa61/CHEM-27-11618-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/39a758479a5c/CHEM-27-11618-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/bddf10bd4697/CHEM-27-11618-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/51a8c638ae63/CHEM-27-11618-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/1f01dd8a1581/CHEM-27-11618-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/daa3545fde76/CHEM-27-11618-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/3d9e1288cd17/CHEM-27-11618-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/e4d84860a9f1/CHEM-27-11618-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf83/8457178/ee00231452dd/CHEM-27-11618-g002.jpg

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