4190-46-9Relevant academic research and scientific papers
PHOTOSTIMULATED REACTIONS OF 1-IODOADAMANTANE AND IODOBENZENE WITH THIOLATE, SELENATE, AND TELLURATE IONS
Palacios, Sara M.,Alonso, Ruben A.,Rossi, Roberto A.
, p. 4147 - 4156 (2007/10/02)
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 kfAdZ/kfPhZ, 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.
The Reactions of Phenylmagnesium Halides with Seleninyl Chloride, Diphenyl Selenoxide, and Dibromodiphenylselenium
Iwama, Yasunori,Aragi, Masashi,Sugiyama, Motohide,Matsui, Kasumi,Ishii,Yasutaka,Ogawa, Masaya
, p. 2065 - 2067 (2007/10/02)
Triphenylselenonium halides were readily prepared in good yields by the one-step reaction of seleninyl chloride with phenylmagnesium halides, followed by treatment with hydrogen halides.The yields of triphenylselenonium halides are markedly affected by the molar ratio of seleninyl chloride to the phenylmagnesum halides.In order to interpret the above results, some probable intermediates, such as diphenyl selenoxide, dibromodiphenylselenium, and diphenyl selenide, were investigated by allowing them to react with phenylmagnesium halides.A pathway which consists of competitive and successive reactions is discussed.
