Unstable intermediates. Part CXLIX. An electron spin resonance study of various phosphinyl radicals formed by solid-state radiolysis

Abstract
One of the major products when a range of trivalent phosphorus compounds was exposed to 60Co γ-rays at 77 K was shown by e.s.r. spectroscopy to be the corresponding phosphinyl radical, ṖR2. These radicals, which include ṖH2, Ṗ(Me2CH)2, Ṗ(OMe)2, Ṗ(SMe)2, ṖPh2, ṖPh(Cl), and ṖCl2, are all characterised by a 31P parallel hyperfine coupling constant in the 240–290 G range and a perpendicular coupling close to zero. The conditions under which these radicals are formed, and the mechanisms involved, are outlined and discussed.

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