Conjugate Of The Theoretical Study Of The Class Generation, Structure And Configuration Of Isomerization Of The Alkene

The mechanism of formation, geometries, and rearrangement of conjugated molecules CH2 = CH-CH=R:LiX(R=C,Si,Ge; X=F,C1) have been studied using the ab initio and density function method (DFT). Geometries, and rearrangement of conjugated molecule HC1N=B: has also been studied in this thesis. The thesis consists of four parts.1. Geometries and Isomerizations of Conjugated molecules CH2 = CH桟H =R:LiF(R=C, Si,Ge;)Structures of conjugated carbenoids of trans- CH2 = CH:CH = C:LiF have been examined in detail by ab initio method at MP2/6-31G** level, obtained three equilibrium geometries and two transition states regarding isomerization reactions between the three geometries. The theoretical analysis indicated that the equilibrium geometries 1 and 3 are the stable structures. Structures of conjugated silylenoids of trans- CH2=CH 桟H=Si:LiF have been also examined in detail by ab initio method at MP2/6-31G** level, and six equilibrium geometries and five transition states regarding isomerization reactions between the six geometries have been obtained. The theoretical analysis indicated that the equilibrium geometries 4 and 3 are the stable structures. Structures of conjugated germylenoids of trans- CH? ?CH桟H ?Ge:LiF have also been examined in detail by ab initio method at B3LYP/6-31G** level too, obtained five equilibrium geometries and four transition states regarding isomerization reactions between the five geometries. The theoretical analysis indicated that the equilibrium geometries 4 and 5 are the stable structures. The characteristics and stability of the involved geometries have been analyzed in terms of the Mtllliken populations, and chemical activities for the equilibrium geometries were also briefly discussed.2. Mechanism of Formation of Conjugated trans- CH2=CH:CH=C:LiClMechanism of formation of conjugated trans- CH2 = CH:CH = C:LiCl by the reaction of CH2=CH - CH-CHCl+CH3Li - CH2 = CH - CH = C.LiCl has been studied in detail by DFT method at B3LYP/6-31G** level. A five-membered cyclic59 李文佐:山东师范大学颐士学位论文structure was formed in the transition state of the reaction. The potential profile for this reaction was obtained by the calculation of IRC.3. The Theoretical Study of the Hydrogen Transfer of CH2 = CH 桟H=C:LiFThe density functional theory(DFT) at B3LYP/6-31G* level was employed to study the hydrogen transfer process of conjugated trans- CH2 = CH ?CH = C:LiF. The reaction undergoes an intermediate and two transition states. A three-membered cyclic structure was formed in the transition states of the reaction .4. Study on the Rearrangement reaction of HC1N=B: Using DFT MethodThe mechanism of the rearrangement reaction of HC1N=B: has been studied using DFT method of quantum chemistry' at B3LYP/6-311G** level. The result shows that the Transition States of the H-transfer and Cl-transfer of the title compound are both three-membered ring structure, and both products are liner molecules. The H-transfer is at internal molecular plane, but the Cl-transfer at the external one. According to the results at B3LYP/6-311G** level, thermodynamic and kinetic properties of the rearrangement reaction have been calculated. The half life of HC1N=B: has been calculated using the rate of reaction HC1N=B:桯-N=B-C1, and the value at 300K is 3.46 X 10"9s.