The Theoretical Study On The Structures And Reaction Of GeR₁R₂MX Germylenoid

As the analogues of carbenoid and silylenoid, GeR₁R₂MX germyleniod can look as the products of germylene and alkali metals. Like the germylene, the germyleniod can take part in many reactions, which is used to synthesize some new organic germanium. Under the proper conditions, germyleniod can be as the van compound, producing germylene. At present there are many reports about the experimental study on the germylene-transition mental compound, but the theoretical study on the form bond, structure and reaction alive have not been reported. However, the experimental study on the alkali metal and halid germyleniod is ignored. Therefore, following the development of the carbenoid and silylenoid, the study on the germyleniod is seriously needed. The main contents of this dissertation are as follows:Chapter 1 is the introduction. In the introduction, the research history on germyleniod in the research background and the innovation are briefly introduced.In chapter 2, the theoretical investigation on the structure and the reactions is performed. All basic theories we used are transition state theory, ab initio, density functional theory and solvent effect.In chapter 3, we calculate the structures and the isomeric reactions of GeR2MX germyleniod. Germyleniod has four basic isomers, P-complex (1),σ- complex (2),three-membered ring (3) and tetrahedron (4). The P-complex is the most stable one and theσ- complex is the least stable one. The contents of this chapter are: At the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels, we calculate the equilibrium structures and the tautomeric transition state of GeH₂LiF, GeH₂LiCl and GeH₂LiBr for the first time, and calculate the vibrational frequencies and infrared intensities. We study on the isomerization of GeH₂LiF germyleniod and analyse the thermodynamics and kinetics for this isomerization reaction. At the same time, we optimize the structures of GeH₂KX, GeH₂NaX and CH4GeLiX, using the B3LYP/6-311++G(3df, 3pd) basis set. In the end, we compare the stability of the structures and analyse the effect from alkali metals, halogen X and group R on the stability and binding energy of R₁R₂GeMX germyleniod.Chapter 4: The solvent effect on the structures and isomerization of GeH₂LiF and GeH₂LiCl. We use Polarized Continuum Model (PCM) of Tomasi to simulate the solvent effect on the structure and isomerization of GeH₂LiF germyleniod and obtain a new structure in the solvent with higher polarity. At the same time, we use Onsager Model to simulate the solvent effect on the structure and isomerization of GeH₂LiCl germyleniod. When the polarity of the solvent is higher, theσ- complex disappears.Chapter 5: The insertion reactions of GeH₂LiF. Like germylene, germyleniod can take part in many reactions, such as addition reaction, insertion reaction and polymerization reaction. Because of the limited time we only study the insertion reaction, the p-complex of GeH₂LiF with the HF, H₂O, PH₃, GeH₄ and CH₄. For getting more data of reactions, we compute the rate constant of insertion reactions using the transition state theory.We make great efforts to get the systemic and accurate results during the study. Actually, many valuable results are obtained. This will guide and promote the development of theoretical and practical study on the germyleniod.