Kinetic Isotope Effects for Hydrogen Abstraction from Various Saturated Hydrocarbons by Deuterium Atoms in the Gas Phase

1986 ◽  
Vol 90 (4) ◽  
pp. 375-382
Author(s):  
Noboru Fujisaki ◽  
Tino Gäumann ◽  
Amanz Ruf
Keyword(s):  
Gas Phase ◽  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Saturated Hydrocarbons ◽  
Kinetic Isotope

Measurements of Solvent and Secondary Kinetic Isotope Effects for the Gas-Phase SN2 Reactions of Fluoride with Methyl Halides

1994 ◽  
Vol 116 (8) ◽  
pp. 3609-3610 ◽  
Author(s):  
Richard A. J. O'Hair ◽  
Gustavo E. Davico ◽  
Jale Hacaloglu ◽  
Thuy Thanh Dang ◽  
Charles H. DePuy ◽  
...  
Keyword(s):  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Methyl Halides ◽  
Sn2 Reactions ◽  
Kinetic Isotope

Hydrogen abstraction from (2H3)methyl acetate by methyl and trifluoromethyl radicals

1981 ◽  
Vol 34 (4) ◽  
pp. 727 ◽  
Author(s):  
NL Arthur ◽  
PJ Newitt
Keyword(s):  
Rate Constants ◽  
Methoxy Group ◽  
Methyl Acetate ◽  
Isotope Effects ◽  
Hydrogen Abstraction ◽  
Kinetic Isotope Effects ◽  
Temperature Range ◽  
Kinetic Isotope ◽  
Acetyl Group

A study of hydrogen abstraction from CH3COOCD3 by CH3 radicals in the temperature range 113-232�, and by CF3 radicals in the range 83-212�, has yielded data on the reactions: CH3+CH3COOCD3 → CH4+CH2COOCD3 (1)CH3+CH3COOCD3 → CH3D+CH3COOCD2 (2) CF3+CH3COOCD3 → CF3H+CH2COOCD2 (3) CF3+CH3COOCD3 → CF3D+CH3COOCD2 (4) The corresponding rate constants, based on the values 1013.34 and 1013.36 cm3 mol-1 s-1 for the recombination of CH3 and CF3 radicals, respectively, are given by (k in cm3 mol-1 s-1 and E in J mol-1): logk1 = (11.31�0.12)-(43500�1030)/19.145T (1) logk1 = (11.31�0.12)-(53460�640)/19.145t (2) logk3 = (11.12�0.06)=(34260�450)/19.145T � (3) logk4 =(10.93�0.12)-(38650�900)/19.145T (4)These results lead to kinetic isotope effects at 400 K for attack on the acetyl group of 11, for the CH3 reaction, and 24, for the CF3 reaction, thus confirming the values we obtained previously. For attack on the methoxy group, the kinetic isotope effects are 8 and 4, for the CH3 and CF3 reactions, respectively.

scholarly journals Deuterium kinetic isotope effects in microsolvated gas-phase E2 reactions

2007 ◽  
Vol 18 (6) ◽  
pp. 1046-1051 ◽  
Author(s):  
Nicole Eyet ◽  
Stephanie M. Villano ◽  
Shuji Kato ◽  
Veronica M. Bierbaum
Keyword(s):  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

Activation of methane by gaseous platinum(II) ions PtX+ (X = H, Cl, Br, CHO)

2005 ◽  
Vol 83 (11) ◽  
pp. 1936-1940 ◽  
Author(s):  
Detlef Schröder ◽  
Helmut Schwarz
Keyword(s):  
Mass Spectrometry ◽  
Key Words ◽  
Electrospray Ionization ◽  
Gas Phase ◽  
Bond Activation ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Methane Activation ◽  
Gas Phase Reactions ◽  
Kinetic Isotope

The gas-phase reactions of methane with the platinum(II) ions PtX+ with X = H, Cl, Br, and CHO are studied by mass spectrometry. The PtX+ ions are generated by electrospray ionization of methanolic solutions of hexachloroplatinic acid and hexabromoplatinic acid, respectively. Small to moderate intramolecular kinetic isotope effects determined for the C—H(D) bond activation of CH2D2 suggest that the activation of methane by gaseous PtX+ cations is subject to thermochemical control by the product channels. In addition, the PtCl2+ cation is also able to activate methane, whereas PtCl3+ is unreactive under the conditions chosen. Key words: gas-phase reactions, mass spectrometry, methane activation, platinum bromide, platinum chloride.

Deuterium kinetic isotope effects on the thermal isomerizations of deuteriocyclopropane to deuterium-labeled propenes

2005 ◽  
Vol 83 (9) ◽  
pp. 1510-1515
Author(s):  
John E Baldwin ◽  
Stephanie R Singer
Keyword(s):  
Key Words ◽  
Gas Phase ◽  
Bond Cleavage ◽  
Isotope Effects ◽  
Reactive Intermediates ◽  
Kinetic Isotope Effects ◽  
Thermal Rearrangement ◽  
Carbon Bond ◽  
Kinetic Isotope ◽  
Carbon Carbon Bond

The gas-phase thermal isomerizations of deuteriocyclopropane to the four possible monodeuterium-labeled propenes have been followed at 435 °C. The observed distribution of products provides estimates of two deuterium kinetic isotope effects, the secondary [Formula: see text] for the carbon–carbon bond cleavage leading to trimethylene diradical reactive intermediates and the primary [Formula: see text] ratio for a [1,2] shift of a hydrogen or deuterium leading from the diradical to a labeled propene. The values determined are [Formula: see text] = 1.09 ± 0.03 and [Formula: see text] = 1.55 ± 0.06. The experimental [Formula: see text] value found agrees well with some, but not all, earlier calculated values and conjectures. Key words: cyclopropane, thermal rearrangement, kinetic isotope effects.

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