Effect of the environment of phosphorus on the distribution of spin density in phosphoniminoxyls

Il'yasov, A. V.; Morozova, I. D.; Vafina, A. A.; Zaripova, R. M.; Balakina, Marina Yu.

doi:10.1007/bf00961348

Cited by 2 publications

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“…The study of the spin density distribution in a series of phosphoniminoxyls [13] R'R2P(0)CR'=NO [R3 = -CH = N-N(CH 3 ) -C(= S) -NH 2 ] on successive substitution of groups R'=RZ =n-BuO by n-Bu showed that in the syn isomer a' significantly decreased ( Table 2). It should be noted that with the replacement of R' by a less electronegative group the stability of iminoxyls markedly decreases.…”

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ESR study of some iminoxy free radicals generated from phosphorylated oximes and dioximes

et al. 1998

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The new type of phosphoniminoxy free radicals was generated electrochemically or by chemical oxidation of oximes. It was established the strong difference of ESR parameters for isomeric Z and E forms of the radicals. The spin distribution and its correlation with electronic and spatial characteristics of molecules as well as with intramolecular interactions are discussed.Iminoxy free radicals are 6-electron radicals with a paramagnetic fragment C=N-O'. It is known [1, 2] that, like the original oximes, iminoxy radicals exist in two isomeric Z and E forms, which are separated by a high energy barrier, making the transition from one form to the other practically impossible:Phosphorus-containing oximes and its iminoxy free radicals are of great interest because of their important specific properties and biological activities. The main peculiarities of these radicals are the large phosphorus hyperfine splitting and its sensitivity to environment and to the media. ESR spectra of these radicals are usually not complicated because of the phosphorus nuclear spin equal to 1/2.Phosphorus-containing iminoxyl radicals of the XP(0)(OR)2C=NO' and [P(0)(OR) 2 ] 2 C=NO' types, described for the first time in [3], were produced as secondary products in photolysis of a solution of 2-methyl-2-nitrosopropane

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confidence: 99%