A variety of mono-substituted aryl primary phosphines, ArPH2, have been modeled using semi-empirical and ab initio methods. Substituents exhibiting electron donating and withdrawing effects, via both induction and resonance, were examined in the ortho, meta, para positions in the pursuit of aryl primary phosphines stabilized by primarily electronic effects alone. SOMO energies of the related radical cations, [ArPH2]+ have been previously used as a reliable predictor for the reactivity of phosphines toward oxygen at atmospheric concentrations. The PM6, PM7 and RM1 methods in MOPAC and HF/MINI, HF/MIDI, and HF/3-21G theory levels in GAMESS were all utilized to identify probable air-stable targets. These methods were benchmarked against an experimentally-backed training set at the B3LYP/6-31G* level of theory.

Computational evaluation of substituent effects on the predicted air-sensitivity of aryl primary phosphines

256th National Meeting (2018)

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