Generation and e.s.r. spectra of some new phosphorus-centred radicals Ṗ2Ar2X, Ṗ(Ar)X, Ṗ(OAr)2, ṖAr2(:O), ṖAr[N(SiMe3)2](:NSiMe3), and [P2Ar2]˙–derived from the bulky group C6H2But3-2,4,6(= Ar)

Abstract

The photochemical reaction of X₂ and the diphosphene trans-ArPPar (Ar = C₆H₂Bu^t ₃), (1) leads successively to Ṗ₂Ar₂X, (2), Ṗ(Ar)X, (3), and upon cooling [(Ar)X]₂[for X = OBu^t, ΔH_diss= 107 ± 7kJ mol^–1] for X = OBu^t or SPrⁿ, whereas for X = SBu^t only (3) was detected; the radicals Ṗ(Ar)X, Ṗ(Oar)₂, and Ṗ₂(:O) were formed by reduction of the appropriate diamagnetic P^III or P^V chloride, while [P₂Ar₂]˙^– was obtained from (1) and Na[C₁₀H₈].