Partial deuteration

The mechanism of the PdCh-catalyzed Cope rearrangement has been studied by use of the partially deuterated 1.5-diene 53[46], The coordination of Pd(II) activates the alkene, and cyclization (carbopalladation) takes place to... 

Figures (a) Scattering geometry for ERS (b) ERS spectrum from 200-A partially deuterated polystyrene on Si, E h 3.0 MeV (adapted from ref. 101 and (cl schematic ERS depth profile spectrum.

The major problem in method (a) is that in ion-molecule interchange, considerable momentum in the direction of travel of the incident ion is imparted to both final products. Hence, in a perpendicular type apparatus only transfer of low weight particles can be observed at all and only at very low velocities of the incident ions (1, 9, 10, 11, 12, 13, 19, 20, 23, 27). Cross-sections cannot be measured. The value of these investigations is that some ion-molecule reactions—e.g., proton transfer and hydride ion transfer—can be identified. The energetics and the competition between charge exchange and ion-molecule reactions can be discussed, and by using partially deuterated compounds, one can obtain a detailed picture of the reaction. 

The occurrence of proton transfer reactions between Z)3+ ions and CHa, C2H, and NDZ, between methanium ions and NH, C2HG, CzD , and partially deuterated methanes, and between ammonium ions and ND has been demonstrated in irradiated mixtures of D2 and various reactants near 1 atm. pressure. The methanium ion-methane sequence proceeds without thermal activation between —78° and 25°C. The rate constants for the methanium ion-methane and ammonium ion-ammonia proton transfer reactions are 3.3 X 10 11 cc./molecule-sec. and 1.8 X 70 10 cc./molecule-sec., respectively, assuming equal neutralization rate constants for methanium and ammonium ions (7.6 X 10 4 cc./molecule-sec.). The methanium ion-methane and ammonium ion-ammonia sequences exhibit chain character. Ethanium ions do not undergo proton transfer with ethane. Propanium ions appear to dissociate even at total pressures near 1 atm. 

Fig. 3.—A. Initial Slope Approximation to Determine the Initial, Nonselective, Spin-Lattice Relaxation Rate of H-S of 2,3 S,6-Di-0-isopropylidene-a-D-mannofuranose (2) in Me2SO-d Solution. (Points between 0.01 and l.SS s were selected for tracing the best straight line.) B. The Same as in A for H-1 of a Partially Deuterated Sample of 1,6-Anhydro- -cellobiose Hexaacetate (3). [Note that the relaxation of H-1 is strongly dependent on the choice of I value. An R (ns) value of 0.24s was obtained from the data points 0 t 5s, where a value of 0.18 s was obtained from the terminal decay 5 lOs (see text).]...

P21212i Z = 4 D = 1.663 R = 0.024 for 1,863 neutron intensities at 123 K. This is a neutron-diffraction, low-temperature refinement of a partially deuterated molecule. The undeuterated molecule had previously been studied by neutron diffraction at room temperature.10 The experiment was performed in order to seek evidence of favored replacement of hydrogen by deuterium at the anomeric hydroxyl group, but no evidence therefor was observed. 

P212121 Z = 4 Dn = 1.540 R = 0.032 for 1,051 neutron intensities at 123 K. This was an experiment similar to that of the partially deuterated / -L-arabinopyranose already described. The results here were also negative. The room-temperature, neutron-diffraction structure of the un-deuterated compound had been determined previously.11... 

Odutola, J. A., and T. R. Dyke. 1980. Partially deuterated water dimers Microwave spectra and structure. J. Chem. Phys. 72, 5062. 

Scheme 1.18. Synthesis of non-deuterated, partially deuterated, and fully deuterated vinyl derivatives via hydrozirconation of terminal alkynes.

The signals in the spectra of the partially deuterated amino acid (Figs. 1.2 b-d and 1.2 f)... 

The 13 C resonances in derivatives of aniline reveal that the carbon bearing a partially deuterated NH2 group appears as a multiplet because of the deuterium isotope effect on the 13C chemical shift, when the hydrogen exchange is low. This effect is larger for... 

Reddy, K. V., Heller, D. F., and Berry, M. J. (1982), Highly Vibrationally Excited Benzene Overtone Spectroscopy and Intramolecular Dynamics of CsH6, C6D6, and Partially Deuterated or Substituted Benzenes, J. Chem. Phys. 76, 2814. 

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