51558-79-3Relevant academic research and scientific papers
Vertical and nonvertical participation by sulfur, selenium, and tellurium
White, Jonathan M.,Lambert, Joseph B.,Spiniello, Marisa,Jones, Scott A.,Gable, Robert W.
, p. 2799 - 2811 (2007/10/03)
The mechanism of stabilization of positive charge on carbon by sulfur, selenium, or tellurium at the: β-position has been investigated kinetically, by measurement of rate enhancements, and structurally, by variation of the bond strength to the leaving group. Stabilization can occur either nonvertically with formation of a bridged intermediate or vertically through hyperconjugation within an open carbocation. We observed large rate enhancements (105 for S, 106 for Se) in 97% aqueous trifluoroethanol with trifluoroacetate as the leaving group. These enhancements are consistent with either mechanism. Product structures also are consistent with either mechanism. Nine crystal structures revealed that the bond to the leaving group (C-O) is lengthened by the presence of S or Se at the β-position, in proportion to the basicity of the leaving group. This lengthening is not accompanied by angle distortions expected for the bridging mechanism. The crystallographic data support vertical (hyperconjugative) character along the reaction coordinate, more so for selenium than sulfur.
Superelectrophilic selenium. A new simple method for generation of areneselenenyl trifluoroacetates and triflates
Kutateladze, Andrei G.,Kice, John L.,Kutateladze, Tatiana G.,Zefirov, Nikolai S.,Zyk, Nikolai V.
, p. 1949 - 1952 (2007/10/02)
Areneselenenyl trifluoroacetates and triflates were obtained by comproportionation of an areneseleninic anhydride with the corresponding diselenide in the presence of trifluoroacetic or triflic anhydride. This represents an attractive alternative to the previously reported1-5 route for preparation of these reagents.
