4960-86-5Relevant academic research and scientific papers
Nuclear Magnetic Resonance Studies on Partially Deuteriated Transition Metal-Methyl Derivatives
Green, Malcolm, L. H.,Hughes, Andrew K.,Popham, Neil A.,Stephens, Adam H. H.,Wong, Luet-Lok
, p. 3077 - 3082 (1992)
Nuclear magnetic resonance studies on show a strong temperature dependence of the isotope shift indicating the presence of a monoagostic methyl group.The magnitude and sign of the geminal coupling constant 2J(H-D) 2J(H-H)> and the isotope shift, together with the temperature dependence of this shift, have been recorded for , (dmpe = Me2PCH2CH2PMe2), nCl5-n> (n = 1-3), (M = Ti, Zr of Hf), (M = Ti or Zr, thf =tetrahydrofuran), , , , (M = Ti, Zr or Hf) and .The isotope shifts for all these complexes are essentially temperature independent.A convenient synthesis of Li(CH2D) is described.
Chlorodefluorination of Fluoromethanes and Fluoroolefins at a Lewis Acidic Aluminum Fluoride
Braun, Thomas,Pan, Xinzi,Scholz, Gudrun,Talavera, Maria
, (2022/03/27)
Chlorodefluorination reactions of fluoromethanes and fluoroolefins catalysed by the highly Lewis acidic nanoscopic aluminum chlorofluoride (ACF, AlClxF3?x, x≈0.05–0.3) in the presence of ClSiEt3 were studied. Both fluoromethanes and fluoroolefins convert under mild reaction conditions by fluorine-chlorine exchange steps into chlorinated fluoro derivatives. MAS NMR studies provided information on the interaction of silanes and hexafluoropropene with the ACF surface.
Kinetic and theoretical study of the hydrodechlorination of CH 4- xClx (x = 1-4) compounds on palladium
Chen, Nan,Rioux, Robert M.,Barbosa, Luis A. M. M.,Ribeiro, Fabio H.
experimental part, p. 16615 - 16624 (2011/10/30)
The reaction kinetics of hydrodechlorination (HDCl) for a series of CH 4-xClx (x = 1-4) compounds were measured on a Pd/carbon catalyst. The rate of HDCl correlated with the C-Cl bond energy, suggesting scission of this bond in the molecularly adsorbed molecule is rate-determining. The measured reaction kinetics of the CH4-xClx compounds support a previously proposed Langmuir-Hinshelwood type reaction mechanism. Kinetic and isotope exchange experiments demonstrated the following: gas phase H2 and HCl are in equilibrium with surface H and Cl; adsorbed Cl is the most abundant surface intermediate; and irreversible scission of the first C-Cl bond is rate-determining. The overall hydrodechlorination reaction rate can be written as kKR-Cl[R-Cl]/(1 + KHCl[HCl]/KH2 1/2[H2]1/2). The activation energy of the rate-determining step was related linearly to the dissociation energy of the first C-Cl bond broken in a Broensted-Evans-Polanyi relationship. This behavior is in agreement with a previous study of CF3CF 3-xClx compounds. During the reaction of CH3Cl, CH2Cl2, and CHCl3 with deuterium, H-D exchange occurred in only 2%, 6%, and 9% of products, respectively. The increasing H-D exchange with Cl content suggests the steps which determine selectivity in these multipath, parallel reactions. The density functional theory (DFT)-calculated activation energies for the dissociation of the first C-Cl bond in the family of chlorinated methane compounds are in good agreement with the values extracted from kinetic modeling, suggesting that parameters estimated from DFT calculations may be used to estimate the reactivity of a particular chlorinated compound within a family of chlorocarbons.
