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I. Study of hydrogen bonding by infrared spectroscopy and nuclear magnetic resonance. II. Electron paramagnetic resonance of Mn(II) complexes in acetonitrile

Citation

Fung, Bing-Man (1967) I. Study of hydrogen bonding by infrared spectroscopy and nuclear magnetic resonance. II. Electron paramagnetic resonance of Mn(II) complexes in acetonitrile. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-09122002-131924

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 <A> 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.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Chan, Sunney I.
Thesis Committee:
  • Unknown, Unknown
Defense Date:4 August 1966
Record Number:CaltechETD:etd-09122002-131924
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-09122002-131924
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3491
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:19 Sep 2002
Last Modified:26 Dec 2012 03:00

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