Phosphoranyl radicals - their structure, formation, and reactions

The influence of phosphorus containing compounds on steam cracking of n-hexane

“…Also, the initiation reaction of a P-containing compound can produce a P-centered radical, P O. This radical may undergo isomerization, forming an O-centered radical PO [32,33]. This reaction is similar to the cis-trans isomerization of olefins since both of their transition state involves the breaking of a p-bond.…”

Persilylated Phosphoranyl Radicals: The First Persistent Noncyclic Phosphoranyl Radicals

“…The t 1/2 of 35 min at 293 K is at least 10 6 times longer than those observed for noncyclic phosphoranyl radicals, and around 10 3 times longer than those reported for the most persistent phosphoranyl radical hitherto ever observed 4. 7, 8 If the S H2 reaction were to be suppressed, a t 1/2 of around 77 min should be observed for radical 6 . Furthermore, the spectroscopic properties of these radicals are well suited for the observation of enhanced DNP effects 18.…”

Ab initio calculations on P?C bond cleavage in phosphoranyl radicals: implications for the biodegradation of organophosphonate derivatives

“…[21][22][23][24] Phosphorus-containing radicals with four substituents on phosphorus are known as phosphoranyl radicals. 26 These inorganic species are typically metastable and many examples have been characterized by electron spin resonance. [27][28][29][30][31][32][33][34][35][36][37][38][39] Phosphoranyl radicals can be produced in biological systems upon radiation damage of the phosphate backbone of cellular genetic material, 26,40 and they have seen extensive theoretical study aimed at understanding their electronic structures and overall geometries as a function of substituents.…”

“…26 These inorganic species are typically metastable and many examples have been characterized by electron spin resonance. [27][28][29][30][31][32][33][34][35][36][37][38][39] Phosphoranyl radicals can be produced in biological systems upon radiation damage of the phosphate backbone of cellular genetic material, 26,40 and they have seen extensive theoretical study aimed at understanding their electronic structures and overall geometries as a function of substituents. 37,[41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57] An interesting question with respect to biological P-C lyase activity has to do with the intrinsic P-C bond strengths in the phosphoranyl radicals derived from either one-electron oxidation or reduction of a given substrate.…”