PHOTOSTIMULATED REACTIONS OF 1-IODOADAMANTANE AND IODOBENZENE WITH THIOLATE, SELENATE, AND TELLURATE IONS

Article abstract of DOI:10.1016/S0040-4020(01)97190-X

The photostimulated reaction of 1-iodoadamantane (1-IAd) with benzenethiolate ion gave the substitution product 1-adamantylphenylsulfide.With benzeneselenate ion (PhSe^-) it gave three products: diphenylselenide, 1-adamantylphenylselenide and di(1-adamantyl) selenide.With benzenetellurate ions it gave the substitution product 1-adamantylphenyltelluride and diphenyltelluride, the latter is ascribed to the photodecomposition of the nucleophile.The photostimulated reaction of 1-IAd with 1-naphtaleneselenate ion only gave the substitution product without scrambling of products.The photostimulated reaction of PhI with 1-adamantaneselenate ion gave the same three products as the reaction of 1-IAd and PhSe^- ion, but with different ratios of products.The reaction with 1-adamantanetellurate ion gave mainly diphenyltelluride, together with the substitution product 1-adamantylphenyltelluride.The relationship of the fragmentation rates of Ad-Z and Ph-Z bonds in radical anions of structure (1-AdZPh)<*>. were studied, and k_fAdZ/k_fPhZ, being Z=S is 3.7, Z=Se is 9.5 and Z=Te is 13.These results suggest that in the photostimulated reactions the products obtained depend on the energy levels of the antibonding ?^* MO and the ?^* MO of the C-Z(Z=S, Se and Te) bonds of the radical anion intermediate.The fragmentation rates of the radical anion intermediates depend on the energy levels of the MO'S involved.