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Abstract: A combined density functional and ab initio quantum chemical study of the insertion reactions of the silylenoid H2SiLiF with GeH3X (X = F, Cl, Br) were carried out. The geometries of all the stationary points for the reactions were optimized using the DFT B3LYP method and then the QCISD method was used to calculate the single-point energies. The results indicated that, there were one precursor complex (Q), one transition state (TS), and one intermediate (IM) which connected the reactants and the products along the potential energy surface. The elucidations of the mechanism of these insertion reactions provided a new reaction mode of silicon–germanium bond formation. [Copyright &y& Elsevier]

Abstract: The insertion reactions of the germylenoid H2GeLiF with CH3X (X = F, Cl, Br) were studied for the first time by using the DFT B3LYP and QCISD methods. The theoretical calculations predicted that along the potential energy surface, there are one precursor complex, one transition state, and one intermediate which connect the reactants and the products. The elucidations of the mechanism of these insertion reactions provide a new reaction mode of germanium–carbon bond formation. [Copyright &y& Elsevier]

Abstract: The H2 elimination reactions of the germylenoid H2GeLiF with RH (R=F, OH, NH2) have been studied by using the DFT B3LYP and QCISD methods. The calculated results indicate that all the mechanisms of the three reactions are identical to each other and under the same condition the H2 elimination reactions should occur easily in the order of H–F>H–OH>H–NH2. In THF solvent the H2 elimination reactions get more difficult than in gas phase. Compared with the insertion reactions of H2GeLiF with RH (R=F, OH, NH2), the H2 elimination reactions have the lower activation barriers and should be more favorable. [Copyright &y& Elsevier]

Abstract: The aluminum chlorogermylenoid H2GeClAlCl2 was studied for the first time by using the DFT B3LYP and QCISD methods in gas phase and in C6H12, THF, DMSO, and H2O solvents. The theoretical calculations predicted that H2GeClAlCl2 has three equilibrium configurations, in which the p-complex is the lowest in energy and is the most stable structure. The isomerization reactions among the three complexes have been investigated. The p-complex is suggested to be the predominant form of H2GeClAlCl2 in the gas phase and in solutions thermodynamically and kinetically. [Copyright &y& Elsevier]

Abstract: The unsaturated germylenoid H2C studied by using the DFT B3LYP method in conjunction with the 6-311+G(d,p) basis set. Geometry optimization calculations indicate that H2C three equilibrium configurations, in which the p-complex is the lowest in energy and is the most stable structure. Two transition states for isomerization reactions of H2C located and the energy barriers are calculated. For the most stable one, vibrational frequencies and infrared intensities have been predicted. [Copyright &y& Elsevier]