Secondary beta-Deuterium Kinetic Isotope Effects in Reactions of Grignard Reagents.
نویسندگان
چکیده
منابع مشابه
Deuterium kinetic isotope effects in microsolvated gas-phase E2 reactions.
This work describes the first experimental studies of deuterium kinetic isotope effects (KIEs) for the gas-phase E2 reactions of microsolvated systems. The reactions of F(-)(H(2)O)(n) and OH(-)(H(2)O)(n), where n = 0, 1, with (CH(3))(3)CX (X = Cl, Br), as well as the deuterated analogs of the ionic and neutral reactants, were studied utilizing the flowing afterglow-selected ion flow tube techni...
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The nucleophilic substitution reactions of Y-O-aryl methyl phosphonochloridothioates with substituted anilines (XC(6)H(4)NH(2)) and deuterated anilines (XC(6)H(4)ND(2)) are investigated kinetically in acetonitrile at 55.0 degrees C. The Hammett and Brønsted plots for substituent (X) variations in the nucleophiles are biphasic concave downwards with a break region between X = H and 4-Cl. The deu...
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M.I.T. Quart. Prog. Rept., 50, 11 (1963); (f) McLean, A. D., J. Chem. Phys., 32, 1959 (1960). 6 Clementi, E., C. Roothaan, and M. Yoshimine, Phys. Rev., 127, 1618 (1962). 7K = 1.75, a(2s)= -0.559 au; a(2p)= -0.312 au; a(H) -0.50 au. 8 For BH a(2s) = -0.909 au; a(2p) = -0.314 au; a(H) = -0.591 au. For BB a(2s) -0.920 au; a(2pr) = -0.189 au; a(2pir) = -0.179 au. 9 Newton, M. D., unpublished work....
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By monitoring the effect of deuterium decoupling on the decay of transverse (15)N magnetization in D-(15)N spin pairs during multiple-refocusing echo sequences, we have determined fast D-D exchange rates kD and compared them with fast H-H exchange rates kH in tryptophan to determine the kinetic isotope effect as a function of pH and temperature.
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Factors influencing the rates of quantum mechanical particle transfer reactions in many-body systems are discussed. The investigations are carried out on a simple model for a proton transfer reaction that captures generic features seen in more realistic models of condensed phase systems. The model involves a bistable quantum oscillator coupled to a one-dimensional double-well reaction coordinat...
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ژورنال
عنوان ژورنال: Acta Chemica Scandinavica
سال: 1992
ISSN: 0904-213X
DOI: 10.3891/acta.chem.scand.46-0985