20875-32-5Relevant academic research and scientific papers
First detection of a selenenyl fluoride ArSe-F by NMR spectroscopy: The nature of Ar2Se2/XeF2 and ArSe-SiMe 3/XeF2 reagents
Poleschner, Helmut,Seppelt, Konrad
, p. 6565 - 6574 (2007/10/03)
Arylselenenyl fluorides ArSeF are obtained from diselenides Ar 2Se2 or arylselenotrimethylsilanes ArSe-SiMe3, and XeF2. They are detected by low-temperature 19F and 77Se NMR spectroscopy. Substitution in the ortho position of the aromatic ring to provide electronic or steric protection is a requirement for their formation. ArSe-F compounds decompose according to 3 ArSe-F → [ArSe-SeF2Ar] + ArSe-F- → ArSeF3 + Ar 2Se2. Reaction energies for this disproportionation as well as that of the sulfur and tellurium homologues have been calculated with MP2, CCSD(T,) and B3 LYP methods. They were found to be increasingly exothermic in the sequence S 77Se and 19F chemical shifts have been calculated by GIAO-MP2 and GIAO-B3LYP methods and are in good agreement with experimental values.
Abnormal Reactions of Overcrowded Tris(arylchalcogeno)silyl Chlorides with Silver Perchlorate
Tokitoh, Norihiro,Imakubo, Tatsuro,Okazaki, Renji
, p. 5819 - 5822 (2007/10/02)
Sterically congested tris(arylchalcogeno)silyl chlorides were synthesized, and their reactions with silver perchlorate afforded unexpected products with a rearranged skeleton which were most likely formed via intermediary tris(arylchalcogeno)silicenium perchlorates.Key Words: silicenium ion; kinetic stabilization; rearrangement; tris(arylchalcogeno)silyl chloride; silver perchlorate
Sterically Hindered Thiolato, Selenolato and Tellurolato Complexes of Mercury(II)
Bochmann, Manfred,Webb, Kevin J.
, p. 2325 - 2330 (2007/10/02)
Mercury(II) complexes of sterically demanding arenechalcogenolato ligands, Hg(EC6H2-2,4,6)2 (E = S or Se; R = Me, Pri or But: E = Te; R = Me or Pri) have been prepared.Whereas complexes carrying smaller aryl substituents (R = Me) are polymeric, those with R = Pri and But form linear two-co-ordinate molecules.For a given R, the volatility of the complexes increases for E = S Pri >> But.
Stabilization of the first selenogermylene as the monomeric pentacarbonyltungsten(0) complex
Du Mont, Wolf-W.,Lange, Lutz,Pohl, Siegfried,Saak, Wolfgang
, p. 1395 - 1399 (2008/10/08)
Bis[(2,4,6-tri-tert-butylphenyl)seleno]germylene, formed in situ by reaction of lithium 2,4,6-tri-tert-butylphenyl selenide with the germanium dichloride dioxane complex, was trapped as the monomeric pentacarbonyl[bis((2,4,6-tri-tert-butylphenyl)seleno)germylene]tungsten(0) complex. Reaction of bis-(2,4,6-tri-tert-butylphenyl) diselenide with the germanium dichloride dioxane complex provides dichlorobis((2,4,6-tri-tert-butylphenyl)seleno)germane. This tetravalent germanium compound and bis-(2,4,6-tri-tert-butylphenyl) diselenide were identified as byproducts when preparation and isolation of the monomeric selenogermylene was attempted. The structure of the selenogermylene tungsten(0) complex was determined from single-crystal X-ray diffraction data. The complex crystallizes (with one toluene per molecule) in the monoclinic space group P21/c with a = 1077.4 (2), b = 1667.2 (2), c = 2880.9 (2) pm, β = 98.33°, and Z = 4. The molecule contains trigonal planar germanium with bonds to tungsten and to two nonequivalent selenium atoms (Ge-Se, 231.4 (2) and 234.6 (2) pm; Ge-W, 252.8 (1) pm). Well-resolved 1H, 13C, and 77Se NMR signals for the two (2,4,6-tri-tert-butylphenyl)seleno groups of the selenogermylene complex indicate hindered rotation around the Ge-Se bonds at room temperature in solution.
Abnormal Reaction of 2,4,6-Tri-t-butylphenyl-lithium with Selenoformates: Possible Intermediacy of Selenobenzaldehyde
Okazaki, Renji,Ishii, Akihiko,Inamoto, Naoki
, p. 71 - 72 (2007/10/02)
The title reaction afforded some products strongly suggestive of the intermediacy of 2,4,6-tri-t-butylselenobenzaldehyde.
Reactions of 2,4,6-Tri-t-butylphenyllithium with O-Alkyl Selenoformates: Intermediate Formation of 2,4,6-Tri-t-butylselenobenzaldehyde
Ishi, Akihiko,Okazaki, Renji,Inamoto, Naoki
, p. 2529 - 2536 (2007/10/02)
2,4,6-Tri-t-butylphenyllithium reacts with O-alkyl selenoformates (1) at three different sites (i.e., the selenoformyl carbon, the selenoformyl hydrogen, and the selenium) to give 1,3,5-tri-t-butylbenzene, 2,4,6-tri-t-butylbenzaldehyde, 6,8-di-t-butyl-3,4-dihydro-4,4-dimethyl-1H-2-benzoselenin (11), bis(2,4,6-tri-t-butylphenylmethyl) di(and tri) selenides, bis(2,4,6-tri-t-butylphenyl) diselenide, and dibutyl diselenide depending on the reaction conditions and the alkyl group in 1.The formation of 11 is explained in terms of the intermediacy of 2,4,6-tri-t-butylselenobenzaldehyde, which is trapped by condensation rection with butylamine leading to N-(2,4,6-tri-t-butylbenzylidene)butylamine.Mechanism for the formation of these products is also discussed.
