Whitesides, George M. (1964) The configurational stability of primary Grignard reagents. Applications of nuclear magnetic resonance spectroscopy to the study of molecular asymmetry. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02102003-082343
The Configurational Stability of Primary Grignard Reagents.
Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 3,3-dimethylbutylmagnesium chloride in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 10 sec.[superscript -1] at room temperature. The dependence of the rate of inversion on solvent and on the structure of the Grignard reagent is discussed in terms of possible mechanisms for the inversion.
Applications of Nuclear Magnetic Resonance Spectroscopy to the Study of Molecular Asymmetry.
The methylene protons of 1-phenylethyl benzyl ether are magnetically non-equivalent and display an AB-type nuclear magnetic resonance spectrum. The variation in the spectrum of this compound and in the spectra of other structurally similar ethers with solvent indicates that the principal contribution to the magnetic non-equivalence of the methylene protons originates in the magnetic anisotropy of the phenyl group bonded directly to the methylene group. It is suggested that the solvent dependence of these spectra reflects changes in the populations of the possible rotational conformations open to the molecule.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||1 January 1964|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||13 Feb 2003|
|Last Modified:||26 Dec 2012 02:30|
- Final Version
See Usage Policy.
Repository Staff Only: item control page