Chemistry and Chemical Biology ETDs

Publication Date

2-23-1979

Abstract

1-13C glycine was studied in nickel(II) solutions using carbon magnetic resonance (CMR). The carboxy bound nickel(II)-glycine complex and the kinetics of complexation between aquated nickel(II) ion and aquated glycine are described. It has been hypothesized that solutions containing no complexation higher than the chelated mono nickel(II)-glycine complex contain five magnetically different glycine species. The effects of these five magnetically different glycine species on the CMR spectra of the nickel(II)-glycine solutions are discussed. The lifetime of the carboxy bound complex is 7.87 x 10-4 sec at 272 K with an activation energy of 9.74 kcal/mole, an activation enthalpy of 9.15 kcal/mole at 298 K, an Arrhenius frequency factor of 8.33 x 1010 sec-1, and an activation entropy of -10.6 cal/mole-deg K. The upfield resonance is attributed mainly to the bidentate or chelated complex. The activation enthalpy for the dissociation of the chelated mono complex is 14.4 kcal/mole. The hyperfine interaction constant, A/h, for this upfield resonance is 5.2 x 105 sec-1 and the linewidth broadening is primarily due to a dipolar relaxation mechanism. CMR resonances for all carbons in the unassociated glycine, the mono, bis, and tris complexes, and in the glycine analogues, betaine hydrochloride, ethylglycinate hydrochloride, and betaine ethylester chloride are reported. The resonances for the meridional and facial isomers of the tris complex are discussed. Some preliminary data on mixed complexes of nickel(II), glycine, and ethylenediamine are reported.

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

William Morris Litchman

Second Committee Member

William Fletcher Coleman

Third Committee Member

Nicholas A. Matwiyoff

Fourth Committee Member

Robert T. Paine Jr.

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