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Intramolecular Hydrogen Bonding in Disubstituted Ethanes. A Comparison of NH···O-and OH···O-Hydrogen Bonding through Conformational Analysis of 4-Amino-4-oxobutanoate (succinamate) and Monohydrogen 1,4-Butanoate (monohydrogen succinate) Anions

Rudner, Mark S. and Jeremic, Senka and Petterson, Krag A. and Kent, David R., IV and Brown, Katherine A. and Drake, Michael D. and Goddard, William A. and Roberts, John D. (2005) Intramolecular Hydrogen Bonding in Disubstituted Ethanes. A Comparison of NH···O-and OH···O-Hydrogen Bonding through Conformational Analysis of 4-Amino-4-oxobutanoate (succinamate) and Monohydrogen 1,4-Butanoate (monohydrogen succinate) Anions. Journal of Physical Chemistry A, 109 (40). pp. 9076-9082. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20150930-125952403

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Abstract

Relative strengths of amide NH···O- and carboxyl OH···O- hydrogen bonds were investigated via conformational analysis of succinamate and monohydrogen succinate anions with the aid of vicinal proton−proton NMR couplings and B3LYP DFT quantum mechanical calculations for a variety of solvents. New experimental results for succinamate are compared with those obtained from previous studies of monohydrogen succinate. While some computational results for monohydrogen succinate were published previously, the results contained herein are the product of a more powerful methodology than that used earlier. The experimental results clearly show that intramolecular hydrogen-bond formation is more favored in aprotic solvents than in protic solvents for both molecules. Furthermore, the preference of the succinate monoanion for the gauche conformation is much stronger in aprotic solvents than that of succinamate, indicating that the OH···O- hydrogen bond is substantially stronger than its NH···O- counterpart, despite the ∼5 kcal cost for formation of the E configuration of the carboxyl group needed to make an intramolecular hydrogen bond. The actual energy differences between formation of internal hydrogen bonds for monohydrogen succinate and succinamate anion were estimated by comparison of the relative values of K_1 of the respective acids in water and DMSO by a procedure first developed by Westheimer. Recent theoretical work with succinamate highlights the necessity of considering substituent orientational degrees of freedom to understand the conformational equilibria of the central CH_2−CH_2 torsions in disubstituted ethanes. Similar methodology is applied here to succinic acid monoanion, by mapping potential-energy surfaces with respect to the CH_2−CH_2 torsional, carboxyl-substituent rotational, and carboxyl−proton E/Z isomeric degrees of freedom. Boltzmann populations were compared with gauche populations estimated from the experimentally determined coupling constants. The quantum mechanical results for succinamate show a much weaker tendency toward hydrogen bonding than for the succinic acid monoanion. However, the theoretical methods employed appear to substantially overestimate contributions from intramolecularly hydrogen-bonded structures for the succinic acid monoanion when compared with experimental results. Natural bond orbital analysis, applied to the quantum mechanical wave functions of fully optimized gauche and trans structures, showed a strong correlation between the population of amide σ^*_(N-H) and carboxyl σ^*_(O-H) antibonding orbitals and apparent hydrogen-bonding behavior.


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http://dx.doi.org/10.1021/jp052925cDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp052925cPublisherArticle
ORCID:
AuthorORCID
Goddard, William A.0000-0003-0097-5716
Additional Information:© 2005 American Chemical Society. Received: June 1, 2005. Publication Date (Web): September 17, 2005. Acknowledgment is made to the donors of the Petroleum Research Fund administered by the American Chemical Society, for support of this research. We are also deeply indebted to the National Science Foundation under grant CHE-0104273, the Summer Undergraduate Research Fellowship Program (SURF) at the California Institute of Technology, the Senior Scientist Mentor Program of the Camille and Henry Dreyfus Foundation, the E. I. Du Pont Company, and Dr. & Mrs. Chester M. McCloskey for their helpful financial assistance. D.R.K. is grateful for support of this research by a graduate fellowship from the Fannie and John Hertz Foundation. The computational resources at the MSC were provided by ARO-DURIP and ONR-DURIP. Other support for the MSC came from DOE, ONR, NSF, NIH, Chevron-Texaco, Nissan, Aventis, Berlex, Intel, and the Beckman Institute.
Funders:
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
NSFCHE-0104273
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
E. I. Du Pont CompanyUNSPECIFIED
Dr. & Mrs. Chester M. McCloskeyUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
NIHUNSPECIFIED
Chevron-TexacoUNSPECIFIED
NissanUNSPECIFIED
AventisUNSPECIFIED
BerlexUNSPECIFIED
IntelUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Record Number:CaltechAUTHORS:20150930-125952403
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150930-125952403
Official Citation:Intramolecular Hydrogen Bonding in Disubstituted Ethanes. A Comparison of NH···O- and OH···O- Hydrogen Bonding through Conformational Analysis of 4-Amino-4-oxobutanoate (succinamate) and Monohydrogen 1,4-Butanoate (monohydrogen succinate) Anions Mark S. Rudner,Senka Jeremic,Krag A. Petterson,David R. Kent, IV,Katherine A. Brown,Michael D. Drake,William A. Goddard, III, and, and John D. Roberts* The Journal of Physical Chemistry A 2005 109 (40), 9076-9082 DOI: 10.1021/jp052925c
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60614
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:30 Sep 2015 22:24
Last Modified:30 Sep 2015 22:24

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