Theses and Dissertations

Issuing Body

Mississippi State University

Advisor

Saebo, Svein

Committee Member

Pittman, Charles U.

Committee Member

Mead, Keith T.

Committee Member

Alley, Earl G.

Date of Degree

5-13-2006

Document Type

Dissertation - Open Access

Major

Chemistry

Degree Name

Doctor of Philosophy

College

College of Arts and Sciences

Department

Department of Chemistry

Abstract

A series of push-pull systems with different electron donors and electron acceptors were investigated. The carbon-carbon double bond rotational barriers for twelve push-pull ethylene derivatives, NH2CH=CHX, NH2H=CHX and -OCH=CHX (acceptors, X = BH2, CN, NO2, and +CH2) were studied by ab initio calculations. The rotational barrier was chosen as a probe for push-pull effects, as push-pull effects would remove electrons from the central double bond. Complete geometry optimizations and calculations of vibrational frequencies were performed for all minima and transition state structures of the twelve systems. The Synchronous Transit-Guided Quasi-Newton (STQN) method was used to search for the transition state structures. The calculations were carried out at B3LYP/6-31++G(d,p) and MP2/6-311++G(d,p) levels of theory. Electron density maps were used to analyze the electron density distribution. The Merz-Singh-Kollman scheme was chosen to calculate electrostatic potential derived charges on atoms. Calculations at the MP2 level suggest that the strongest push-pull effects result from +CH2 with barriers (to conversion to the transorms) of 10.6, 13.2, and 7.3 kcal/mol for NH2CH=CHCH2+, NH2H=CHCH2+, and -OCH=CHCH2+, respectively. These barriers are about 6, 5, and 9 times smaller than that of ethylene at the same level of theory, respectively. Among the other electron acceptors studied, BH2 was stronger than the cyano and nitro substituents but weaker than CH2+. Solvent effects were examined for the NH2CH=CHX system, X = BH2, CN, NO2, and +CH2 with water and dichloromethane as solvents. Calculations were performed at the B3LYP/6-31++G(d,p) level of theory using three different approaches, the Conductor-like Screening Model (COSMO), the Polarizable Continuum Model (PCM) and the Super-Molecular Approach (SMA). When the solvent is water, SMA calculations retained the barrier-height order of gas phase calculations, while COSMO and PCM reversed the order of BH2 and NO2. Results from this research confirm that both solvents lowered the rotational barriers in all cases. The more polar solvent decreases the rotational barrier more than the less polar solvent due to the existing of a dipolar or charge separated transition states of the push-pull systems.

URI

https://hdl.handle.net/11668/17503

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