Possible skeletal transformations of pyridine and phosphinine during their thermal isomerization

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Resumo

Based on the properties of the of p-electron conjugated system in cyclic polyenes, possible spatial structures of the transition states of the thermal isomerization reactions of pyridine and phosphinine in an oxygen-free atmosphere were found. The existence of transition states is determined by different levels of the stabilization effect of the p-electron conjugation. The determination of the spatial and electronic characteristics of the transition states of pyridine and phosphinine was carried out by the DFT/B3LYP/6-31G* method. Schemes were constructed and potential barriers of the thermal isomerization reactions of pyridine and phosphinine were calculated. A study of the reactivity of the pyridine and the phosphinine in thermal isomerization processes showed a decrease in the degree of aromaticity of phosphinine compared to pyridine.

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Sobre autores

O. Tomilin

National Research Mordovia State University

Email: rodionova_j87@mail.ru
ORCID ID: 0000-0002-1570-230X
Rússia, ul. Bolshevistskaya, 68B, Saransk, 430005

L. Fomina

National Research Mordovia State University

Email: rodionova_j87@mail.ru
ORCID ID: 0000-0002-3971-6714
Rússia, ul. Bolshevistskaya, 68B, Saransk, 430005

E. Rodionova

National Research Mordovia State University

Autor responsável pela correspondência
Email: rodionova_j87@mail.ru
ORCID ID: 0000-0001-7921-2732
Rússia, ul. Bolshevistskaya, 68B, Saransk, 430005

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2. Fig. 1. Example of isospectral graphs for [6]-annulene

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3. Fig. 2. Isospectral graphs C5H5X (X = N, P)

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4. Fig. 3. Structural formulas of valence-conformational isomers of pyridine (phosphinine)

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5. Fig. 4. Spatial structures and values ​​of the total energy of the ground and transition states of C5H5X molecules (X = N, P), generated by molecular graphs with different numbers L. The values ​​of the total energy of the ground and transition states of phosphinine are indicated in italics.

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6. Fig. 5. Paths of possible skeletal transformations of pyridine

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7. Fig. 6. Pathways of possible skeletal transformations of phosphinine

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