Accession Number:

AD0488343

Title:

CATIONIC PERTURBATIONS OF SPIN DENSITIES IN ANION FREE RADICALS

Descriptive Note:

Master's thesis

Corporate Author:

NAVAL POSTGRADUATE SCHOOL MONTEREY CA

Personal Author(s):

Report Date:

1966-05-01

Pagination or Media Count:

124.0

Abstract:

In an investigation of cationic perturbations of spin densities in anion free radicals, as disclosed by variations in proton coupling constants, the EPR spectra of anion free radicals of benzophenone, biphenyl, anthracene, terephthalonitrile and hexacyanobenzene were observed. Radicals were prepared in vacuo, using a vacuum electrolytic cell andor sodium reductions in tetrahydrofuran solution. The spectra of the anthracene and terephthalonitrile radicals, prepared by reduction with sodium in tetrahydrofuran, displayed sodium splitting. It was observed that the coupling constants for protons and nitrogens in the terephthalonitrile radical were smaller in the presence of sodium ion than in the presence of tetra-n-butyl ammonium perchlorate. It was observed that the addition of tetra-n-butyl ammonium perchlorate to sodium-reduced solutions of anthracene or terephthalonitrile removed the sodium coupling, giving narrow- line EPR spectra identical with those obtained by electrolysis in vacuo. Coupling constants for the radicals were determined by a least-squares analysis of the envelope of the central portion of the spectrum, marking field intervals with an NMR field-tracking gaussmeter and utilizing a computer program which synthesizes on EPR spectrum when given coupling constants and other parameters.

Subject Categories:

  • Organic Chemistry
  • Electricity and Magnetism
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE