caa a22 4500 60551268X CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2640-2 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2640-2 Insight into the substitution reactions of silylenoid H2SiLiF with GeH3X (X = F, Cl, Br): a theoretical study [Elektronische Daten] [Bingfei Yan, Wenzuo Li, Cuiping Xiao, Qingzhong Li, Jianbo Cheng] The unique substitution reactions of the three-membered-ring silylenoid H2SiLiF with GeH3X (X = F, Cl, Br) were investigated using ab initio and density functional theory calculations. All stationary points on the potential energy surfaces were optimized at the B3LYP/6-311 + G (d, p) level of theory and the QCISD method was then used to calculate the single-point energies. Theoretical calculations predicted that the substitution reactions of H2SiLiF with GeH3X proceed via two reaction paths (I and II), while forming the same product H2FSi-GeH3. In either pathway, there is one precursor complex (Q), one transition state (TS), and one intermediate (IM) connecting the reactants and products. The substitution reaction barriers of H2SiLiF with GeH3X for path I (48.49, 42.71, and 38.71kJmol−1) decreased with the increase for the same-family element X from up to down in the periodic table, whereas the substitution barriers for path II (6.51, 22.04, and 23.62kJmol−1) increased with the increase in atomic number of X (X = F, Cl, Br). Path II was more favorable than path I. All the substitution reactions of H2SiLiF with GeH3X were exothermic. The elucidation of the unique mechanism of these substitution reactions suggests a new reaction mode of silicon-germanium bond formation. Springer-Verlag Berlin Heidelberg, 2015 Silylenoid H2SiLiF nationallicence Substitution reaction nationallicence GeH3X (X = F, Cl, Br) nationallicence B3LYP nationallicence QCISD nationallicence Yan Bingfei The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut Li Wenzuo The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut Xiao Cuiping The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut Li Qingzhong The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut Cheng Jianbo The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-8 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2640-2 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2640-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Yan Bingfei The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut NATIONALLICENCE 700 1- Li Wenzuo The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut NATIONALLICENCE 700 1- Xiao Cuiping The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut NATIONALLICENCE 700 1- Li Qingzhong The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut NATIONALLICENCE 700 1- Cheng Jianbo The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, 264005, Yantai, People's Republic of China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-8 1610-2940 21:4<1 2015 21 894