Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

Abstract

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPri)2 and the complex (η2-C60)Os(CO)(PPh3)2(CNBut) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (η2-C70)Os(CO)(PPh3)2(CNBut) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C70 with the phosphoryl radicals, which were formed directly from C70 and from the radical adducts of η2-C70)Os(CO)(PPh3)2(CNBut) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.