Richard Gay

Publication Date

1980

Document Type

Dissertation/Thesis

First Advisor

Vanderkooi, Garret

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry

LCSH

Esters; Hydrogen bonding; Organophosphorus compounds

Abstract

Hydrogen bonding of dimethylphosphate anion (DMP) and dimethyl phosphoric acid (DMPH) with water, methanol, and methylamine was studied using the CNDO/2 molecular orbital method. The computed lengths of 0-H-**0 hydrogen bonds involving the phosphate group were significantly shorter than were the computed values for non-phosphate 0-H***0 bonds, in agreement with experiment. The lowest energy for the monohydration of DMP or DMPH was obtained for the linear hydrogen bond in which the atoms of water were coplanar with the anionic oxygens of the phosphate group. The hydrogen bond strengths of methanol and water with DMP or DMPH were of comparable magnitude, but the N-H*••0 bond involving methylamine and DMP was about 25% weaker. The C-H***0 interaction between the methyl group of methanol or methylamine and the phosphoryl oxygen was also examined and found to have all the characteristics (bond strength, charge transfer, and atomic polarization) of a hydrogen bond. The computed bond strength for H0CH3*»*DMP was -7.1 kcal/mole, as compared to -21.8 kcal/mole for a conventional CH30H‘**DMP hydrogen bonding interaction.

Comments

Includes bibliographical references.

Extent

vii, 91 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type

Text

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