80650-90-4Relevant academic research and scientific papers
INVERSION OF REACTIVITY OF THIOLS IN AdN REACTIONS OF ACETYLENES
Bodrikov, I. V.,Korshunov, S. P.,Bazhan, L. I.,Statsyuk, V. E.,Korzhova, N. V.
, p. 610 - 614 (2007/10/02)
The rate of the reaction of arenethiols with diarylpropynones in the presence of triethylamine is described by a second-order kinetic equation (first in each of the reagents).The effect of the substituent in the aromatic ring of the thiol on the reaction rate is opposite in the regions of low (ρ2 > 0) and high (ρ2 1 (with respect to the substrate) is not inverted.According to the quantum-chemical calculations, the inversion of the reactivity of the thiols is due to a change in the forms in which the reagent participates with variation in the concentration of the catalyst and an associated change in the ratio of the attractive and repulsive interactions between the orbitals of the reagents.
12-Te-5 Pertelluranes from 1,2-Oxatellurolyl-1-ium Halides. Synthesis, Structure, and Reactivity. The Quest for Delocalization in 10-Te-3 Telluranes and 12-Te-5 Pertelluranes of Thiathiophthene Structure
Detty, Michael R.,Luss, Henry R.,McKelvey, John M.,Geer, Susan M.
, p. 1692 - 1700 (2007/10/02)
The oxidative addition of chlorine or bromine to 1,2-oxatellurolyl-1-ium chlorides or bromides, respectively, at 0 deg C occurs rapidly to give 12-Te-5 pertelluranes.The structure of 3,5-diphenyl-1,2-oxatellurolylium tribromide (9) was determined unambiguously by single-crystal X-ray crystallographic analysis.Pertelluranes were neutral in solution (CH2Cl2), as determined by conductance studies.The pertelluranes were easily reduced electrochemically to halide ions and the oxatellurolylium halide and were susceptible to nucleophilic attack by Michael addition on the enone segment.Spectroscopic and crystallographic comparison of the pertelluranes with the corresponding oxatellurolylium halides and of dioxatellurapentalenes with the corresponding pertellurane analogues suggested ionic bonding between Te and the halides or O for all four of these systems.Theoretical treatment with CNDO/2 calculations by the program GEOMORV suggested ionic bonding of O and halides to the Te with little ?-delocalization involving Te-O and Te-C bonds in both the tellurane and pertellurane systems.A low-lying ?* LUMO in the pertelluranes was predicted, consistent with the susceptibility to nucleophilic attack, as observed experimentally.
