31704-09-3Relevant academic research and scientific papers
Reactivity of the triple ion and separated ion pair of tris(trimethylsilyl) methyllithium with aldehydes: A RINMR study
Jones, Amanda C.,Sanders, Aaron W.,Sikorski, William H.,Jansen, Kristin L.,Reich, Hans J.
, p. 6060 - 6061 (2008/12/20)
Low-temperature rapid-injection NMR (RINMR) experiments were performed on tris(trimethylsilyl)methyllithium. In THF/Me2O solutions, the separated ion (1S) reacted faster than can be measured at -130 °C with MeI and substituted benzaldehydes (k ≥ 2 s-1), whereas the contact ion (1C) dissociated to 1S before reacting. Unexpectedly, the triple ion reacted faster with electron-rich benzaldehydes relative to electron-deficient ones. The addition of HMPA had no effect on the rate of reaction of the triple ion with p-diethylaminobenzaldehyde, and the immediate product of the reaction was the HMPA-solvated separated ion 1S, with the Peterson product forming only slowly. Thus, the aldehyde is catalyzing the dissociation of the triple ion. HMPA greatly decelerated the reaction of 1S (-10), providing an estimate of the Lewis acid activating effect of a THF-solvated lithium cation in an organolithium addition to an aldehyde. Copyright
Properties of Chalcogen-Chalcogen Bonds, XVII. - Di- and Trisulfanes with Sterically Congested Alkyl Substtuents: The First trans-Dialkyldisulfane
Ostrowski, Martin,Jeske, Joerg,Jones, Peter G.,Mont, Wolf-Walther du
, p. 1355 - 1360 (2007/10/02)
Bistrisulfane (1) is obtained from tris(trimethylsilyl)methyllithium and sulfur with subsequent oxidation by oxygen or from tris(trimethylsilyl)methanethiol with sulfur dichloride.The solid trisulfane contains a transoid (helical) C-S-S-S-C backbone without severe distortion from steric strain.Desulfuration of the byproduct bistetrasulfane (2) with mercury provides 1, but further desulfuration of 1 to bisdisulfane (3) has not been achieved. 3 was isolated after oxidation of lithium tris(trimethylsilyl)methanethiolate with bromine. 3 contains a trans-C-S-S-C moiety with an unusually long S-S bond (210-211 pm).The less crowded bis(triphenylmethyl)disulfane (4) contains a "normal" C-S-S-C moiety with anticlinal conformation (torsion angle -110 deg). Key Words: Disulfanes / Trisulfanes / Bond conformations, S-S
SILA PUMMERER REARRANGEMENT IN HIGHLY STERICALLY HINDERED ORGANOSILICON COMPOUNDS: A NEW ROUTE TO BIS(TRIMETHYLSILYL)KETONE
Ricci, Alfredo,Innocenti, Alessandro Degl',Ancillotti, Monica,Seconi, Giancarlo,Dembech, Pasquale
, p. 5985 - 5988 (2007/10/02)
The oxidation of the tris(trimethylsilyl)methylthio-methane with m-chloroperoxybenzoic acid, leads through a sila-Pummerer rearrangement occuring in unusually mild conditions, to bis(trimethylsilyl)ketone,
BIS(TRIMETHYLSILYL)THIOKETONE
Ricci, Alfredo,Degl'Innocenti, Alessandro,Fiorenza, Mariella,Dembech, Pasqualle,Ramadam, Nazmi,et al.
, p. 1091 - 1092 (2007/10/02)
Tris(trimethylsilyl)methylsulphenylbromide undergoes facile Me3SiBr elimination to give bis(trimethylsilyl)thioketone.
