3219-63-4Relevant articles and documents
Variable pathways for oxygen atom insertion into metal-carbon bonds: The case of Cp*W(O)2(CH2SiMe3)
Mei, Jiajun,Carsch, Kurtis M.,Freitag, Cody R.,Gunnoe, T. Brent,Cundari, Thomas R.
, p. 424 - 435 (2013)
CpW(O)2(CH2SiMe3) (1) (Cp* = η5-pentamethylcyclopentadienyl) reacts with oxygen atom donors (e.g., H2O2, PhIO, IO4-) in THF/water to produce TMSCH2OH (TMS = trimethylsilyl). For the reaction of 1 with IO4-, the proposed pathway for alcohol formation involves coordination of IO4- to 1 followed by concerted migration of the -CH2TMS ligand to the coordinated oxygen of IO4- with concomitant dissociation of IO 3- to produce Cp*W(O)2(OCH 2SiMe3) (3), which undergoes protonolysis to yield free alcohol. In contrast to the reaction with IO4-, the reaction of 1 with H2O2 results in the formation of the η2-peroxo complex Cp*W(O)(η2-O 2)(CH2SiMe3) (2). In the presence of acid (HCl) or base (NaOH), complex 2 produces TMSCH2OH. The conversion of 2 to TMSCH2OH catalyzed by Br?nsted acid is proposed to occur through protonation of the η2-peroxo ligand, which facilitates the transfer of the -CH2TMS ligand to a coordinated oxygen of the η2-hydroperoxo ligand. In contrast, the hydroxide promoted conversion of 2 to TMSCH2OH is proposed to involve hydroxide coordination, followed by proton transfer from the hydroxide ligand to the peroxide ligand to yield a κ1-hydroperoxide intermediate. The migration of the -CH2TMS ligand to the coordinated oxygen of the κ1-hydroperoxo produces an alkoxide complex, which undergoes protonolysis to yield free alcohol.
Energetic Sila-Nitrocarbamates: Silicon Analogues of Neo-Pentane Derivatives
Axthammer, Quirin J.,Klap?tke, Thomas M.,Krumm, Burkhard,Reith, Thomas
, p. 4683 - 4692 (2016/05/24)
Four silanes based on the neo-pentane skeleton Me4-xSi(CH2R)x containing carbamate groups (x = 1-4, R = OC(O)NH2) have been prepared via the corresponding alcohols Me4-xSi(CH2OH)x, starting from the chlorosilanes Me4-xSiClx. Subsequent nitration leads to the corresponding primary nitrocarbamates (R = OC(O)NHNO2), examined for the purpose as potential energetic materials, including the silicon analogue of pentaerythritol tetranitrocarbamate (sila-PETNC) and a siloxane based nitrocarbamate side-product. All compounds were thoroughly characterized by spectroscopic methods including X-ray diffraction. Thermal stabilities and sensitivities toward impact and friction were examined, as well as detonation values by calculating energies of formation using the EXPLO5 V6.02 software.
Synthesis and characterization of alkylsilane ethers with oligo(ethylene oxide) substituents for safe electrolytes in lithium-ion batteries
Zhang, Lingzhi,Lyons, Leslie,Newhouse, Jocelyn,Zhang, Zhengcheng,Straughan, Megan,Chen, Zonghai,Amine, Khalil,Hamers, Robert J.,West, Robert
supporting information; experimental part, p. 8224 - 8226 (2011/06/21)
Alkylsilane ethers, containing one or three carbon spacer groups between the silicon atom and oligo(ethylene oxide) moiety, were designed and synthesized. These compounds are non-hydrolyzable and less flammable than their alkoxysilane counterparts. A full cell test using them as electrolyte solvents showed good cycling performance in lithium-ion batteries.
