Solvent Isotope Effects on the Chemical Shifts of Complex Fluoro Ions in H2O and D2O Solutions

1971 ◽  
Vol 54 (10) ◽  
pp. 4509-4510 ◽  
Author(s):  
K. Radley ◽  
L. W. Reeves
Keyword(s):  
Chemical Shifts ◽  
Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

scholarly journals 45Scandium NMR Investigations in Aqueous Solutions

1983 ◽  
Vol 38 (3) ◽  
pp. 317-321 ◽  
Author(s):  
E. Haid ◽  
D. Köhnlein ◽  
G. Kössler ◽  
O. Lutz ◽  
W. Messner ◽  
...  
Keyword(s):  
Aqueous Solutions ◽  
Chemical Shifts ◽  
Isotope Effects ◽  
Larmor Frequency ◽  
Relaxation Rates ◽  
Nmr Chemical Shifts ◽  
Typical Behaviour ◽  
Solvent Isotope ◽  
Scandium Chloride ◽  
Solvent Isotope Effects

Abstract45Sc NMR chemical shifts, linewidths, and longitudinal relaxation rates have been measured in aqueous solutions of scandium chloride and sulphate as a function of the appropriate acid. A common typical behaviour of these parameters without sudden changes has been observed. Also signals in the basic range have been obtained. H2O -D2O solvent isotope effects on Larmor frequency and relaxation rates are presented.

Solvent isotope effects on chemical shifts of ions in aqueous solutions

1968 ◽  
pp. 214 ◽  
Author(s):  
A. Loewenstein ◽  
M. Shporer ◽  
P. C. Lauterbur ◽  
J. E. Ramirez
Keyword(s):  
Aqueous Solutions ◽  
Chemical Shifts ◽  
Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

scholarly journals Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions

2021 ◽  
Vol 22 (14) ◽  
pp. 7394
Author(s):  
Kyoung Ho Park ◽  
Mi Hye Seong ◽  
Jin Burm Kyong ◽  
Dennis N. Kevill
Keyword(s):  
Rate Constants ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Carbonyl Sulfide ◽  
Activation Parameters ◽  
Chloride Ions ◽  
Reaction Channels ◽  
Decomposition Pathway ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.

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