Effect of the polarity of the medium on the ionic radiation-induced polymerization of elemental (white) phosphorus

Role of reaction media in "green" radiation-induced polymerization of white phosphorus

“…This conclusion is consistent with our earlier results [9], in particular, the data on 31 P NMR spectra, and the quantum-chemical calculations of the P 4 -C 6 H 6 system [10,11].…”

“…Compound (ion) Solvated electron Hydrogen atom Hydroxyl radical Tetraphenyl-phosphonium ion (1.6 ± 0.3) × 10 10 (1.5 ± 0.3) × 10 9 (3.0 ± 0.3) × 10 9 Pyrrolidonium ion (7.5 ± 1.5) × 10 6 -5.7 × 10 9 Imidazolium ion (3.8 ± 0.5) × 10 9 --Benzene (1.2 ± 0.2) × 10 7 (9.0 ± 2.0) × 10 8 (5.2 ± 1.5) × 10 9…”

Quantitative analysis of bonding in P4 clusters

“…Unfortunately, the absence of the uniform detailed analysis of electronic properties of the neutral and ionic phosphorus clusters does not allow us to judge from the experimental results of white phosphorus polymerization [16]. Meanwhile, one might suggest that various allotropic modifications of the elemental phosphorus are caused by its unique electronic system.…”

Elemental Phosphorus and Electromagnetic Radiation

“…The first mechanism suggested for the transformation of white phosphorus into the red allotrope was the symmetric cleavage of the P 4 molecule followed by the recombination of the resulting P 2 unit into the final polymeric red phosphorus (P n ),14 whereas the transformation in nonpolar media (benzene, halohydrocarbons and n ‐hexane) was suggested to occur through a radical mechanism 15c,15d. It was also observed that the gas that resulted from heating white phosphorus at 1000–1500 °C under an inert atmosphere is an equilibrium between P 4 and P 2 molecules (Scheme , path f)17 but the P 4 molecule in solution photolyzes into P 2 at room temperature 18…”