biostudies-literatureUnknown15(17)Sabet-Sarvestani HThis study focuses on the reaction mechanisms involving triphenylphosphine (PPh₃) derivatives, benzyne, and CO₂, giving mechanistic insights into two competing pathways: Path a, which involves direct C-P bond formation, and Path b, which progresses <i>via</i> a [2 + 2] cycloaddition. Comprehensive computational analysis by energy decomposition analysis (EDA) and deformation density insights was employed to elucidate the electronic and steric factors influencing the reactivity and selectivity of PPh₃ derivatives. The results reveal that Path b is energetically and kinetically favored. In Path a, substantial repulsive interactions (Δ<i>E</i> _rep), especially for electron-withdrawing substituents, hinder C-P bond formation, making this pathway unfavRSC advances12917-12930https://www.ebi.ac.uk/biostudies/studies/S-EPMC12013607biostudies-literatureExploring CO&lt;sub&gt;2&lt;/sub&gt; activation mechanisms with triphenylphosphine derivatives: insights from energy decomposition and deformation density analyses.PMC12013607Hosseini FSabet-Sarvestani HHosseini HEshghi HSeddighi MJBolourian SfalseExploring CO&lt;sub&gt;2&lt;/sub&gt; activation mechanisms with triphenylphosphine derivatives: insights from energy decomposition and deformation density analyses.This study focuses on the reaction mechanisms involving triphenylphosphine (PPh₃) derivatives, benzyne, and CO₂, giving mechanistic insights into two competing pathways: Path a, which involves direct C-P bond formation, and Path b, which progresses <i>via</i> a [2 + 2] cycloaddition. Comprehensive computational analysis by energy decomposition analysis (EDA) and deformation density insights was employed to elucidate the electronic and steric factors influencing the reactivity and selectivity of PPh₃ derivatives. The results reveal that Path b is energetically and kinetically favored. In Path a, substantial repulsive interactions (Δ<i>E</i> _rep), especially for electron-withdrawing substituents, hinder C-P bond formation, making this pathway unfav2025-01-01T00:00:00Z2025 Apr2025-07-02T03:04:54.091Z2025-07-02T03:04:54.091ZS-EPMC120136074027140910.1039/d5ra00804b