computational investigation of the effect of substitution on the philicity and stability of carbenes 1,3-disubstituted diphosphole-2-ylidene and 1,3-diaryldiphosphole-2-ylidene based on DFT

Shiri, Azam; Yaghoobi, Fereshteh; Sprim, Azam; Akhondi, Sepide

doi:10.22036/cr.2024.471747.1257

computational investigation of the effect of substitution on the philicity and stability of carbenes 1,3-disubstituted diphosphole-2-ylidene and 1,3-diaryldiphosphole-2-ylidene based on DFT

Document Type : Original Article

Authors

Azam Shiri ¹

Fereshteh Yaghoobi ²

Azam Sprim ³

Sepide Akhondi ³

¹ Department of chemistry. Faculty of science. Malayer university. Malayer. Iran

² Department of Chemistry, Nahavand Higher Education Complex, Bu-Ali Sina University, Hamedan, Iran

³ Department of Applied Chemistry, Faculty of Science, Malayer University, Malayer 65719-95863, Iran

10.22036/cr.2024.471747.1257

Abstract

In this article, the effect of various substitutions on the philicity and stability of carbenes, 1,3-disubstituted diphosphole-2-ylidene and 1,3-diaryldiphosphole-2-ylidene was evaluated based on Density functional theory calculations in both gas and solvent phases. The global electrophilicity parameter was used to obtain philicity and parameters such as the energy gap between singlet and triplet states the energy of hydrogenation the energy of isodesmic reaction and the energy difference between HOMO and LUMO levels were used to calculate stability and the results were then compared with each other. In 1,3-disubstituted diphosphole-2-ylidenes, the species with the NO2 group has the highest electrophilic value and the lowest stability, whereas the carbene with the t-Bu has the most nucleophilic character and the highest stability in two both phases. In the case of 1,3-diaryldiphosphole-2-ylidenes, the species with the NH2 and NO2 groups have the highest nucleophilicity and highest electrophilicity, respectively. Generally, the stability of 1,3-diaryldiphosphole-2-ylidenes is higher than that of 1,3-disubstituted phosphole-2-ylidenes. For a better and more complete investigation, using NBO analysis, bond order was also calculated for these compounds. The bond order between the carbene center and phosphorus is shorter than the P-C single bond, indicating strong electron pair donation from phosphorus to the carbene center.

Graphical Abstract

Keywords

Carbene

Electrophilicity

Nucleophilicity

Phosphorus

Stability

Subjects

Organic Chemistry

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