I. Study of Hydrogen Bonding by Infrared Spectroscopy and Nuclear Magnetic Resonance. II. Electron Paramagnetic Resonance of Mn(II) Complexes in Acetonitrile

Author: Fung, Bing-Man

Year: 1967

Degree: Dissertation (Ph.D.)

Advisor: Chan, Sunney I.

Committee Member: Unknown, Unknown

Option: Chemistry; Physics

DOI: 10.7907/38M4-4C81

Abstract

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Part I.

The infrared and near infrared spectra of acetic acid, d [subscript 3-] acetic acid, acetic acid-d, formic acid, d-formic acid, formic acid-d, HOD and methanol have been studied in several organic solvents. The solvents used were acetone, acetonitrile, dimethylsulfoxide, dioxane, tetrahydrofuran and their perdeuterated analogues. The spectra were characterized on the basis of the formation of 1-1 hydrogen bonded complexes between the proton donors and the solvent molecules. A one-dimensional double minimum potential function was developed and then calculated for each hydrogen bonded complex. The principles of treating the problem in a more complete way, namely, including the interaction between the A-H vibration and the A-B vibration in the complex A-H...B, were outlined.

The nuclear magnetic resonance of the hydroxyl proton of acetic acid dissolved in acetone, dimethylsulfoxide, dioxane and tetrahydrofuran has been investigated. The results are discussed in terms of the equilibria between the acid monomer, the acid dimer and the acid-solvent complex in dilute solutions of acid. The equilibrium constant for each system and the hydroxyl proton chemical shift for the hydrogen bonded complexes were obtained.

The infrared and near infrared spectra and the nuclear magnetic resonance of the hydrogen biacetate anion have been studied. Potential curve, equilibrium constant and proton chemical shift for this species were calculated.

Part II.

Electron paramagnetic resonance for Mn(II) was studied in the systems Mn(ClO[subscript4])[subscript 2] in acetonitrile. The g value and hyperfine interaction constant were determined for the complexes Mn(CH[subscript 3]CN)[subscript 6][superscript ++], MnCl[subscript 4][superscript=], MnBr[subscript 4][superscript=]. Computer-simulated e.s.r. spectra were obtained and compared with the experimental spectra.

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