An ab initio study on the stability of isolated phosphaalkene synthons

Adrianna Cyraniak; Sylwia Freza; Piotr Skurski

doi:10.1039/d3cp03770c

An ab initio study on the stability of isolated phosphaalkene synthons

Phys Chem Chem Phys. 2023 Oct 18;25(40):27196-27203. doi: 10.1039/d3cp03770c.

Authors

Adrianna Cyraniak¹, Sylwia Freza¹, Piotr Skurski^{1

2}

Affiliations

¹ Laboratory of Quantum Chemistry, Department of Theoretical Chemistry, Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308 Gdańsk, Poland. piotr.skurski@ug.edu.pl.
² QSAR Lab Ltd., Trzy Lipy 3, 80-172 Gdańsk, Poland.

PMID: 37789824
DOI: 10.1039/d3cp03770c

Abstract

Using ab initio methods and flexible basis sets, we examined the electronic, geometric, and thermodynamic stabilities of selected phosphaalkene synthons matching the (PCR₂)^- formula (R = H, CH₃, C₆H₅, C₆F₅, and Mes). All isolated synthons considered were found to be electronically stable and susceptible to neither fragmentation nor isomerization processes. The structures corresponding to the most stable isomers of the studied phosphaalkene synthons contain a PC double-bond (whose presence was confirmed by natural bond orbital occupancies of σ(P-C) and π(P-C) approaching 2 electrons) and two R substituents connected to the carbon atom in either (PCR₂)^- (for R = H, CH₃, C₆H₅, and Mes) or (PCF-R-R)^- (for R = C₆F₅) manner. Vertical electron detachment energies (spanning the 0.924-3.118 eV range) characterizing the phosphaalkene synthons were predicted and discussed.