Theoretical studies on the imine germylenoid HNdouble bond; length as m-dashGeNaF and its insertion reaction with R–H (R = F, OH, NH2, CH3)

The geometries and isomerization of the imine germylenoid HNdouble bond; length as m-dashGeNaF as well as its insertion reactions with R–H (R = F, OH, NH2, CH3) have been systematically investigated at the B3LYP/6-311+G∗ level of theory. The potential barriers of the four insertion reactions are 117.2, 172.6, 219.7, and 322.3 kJ/mol, respectively. Here, all the mechanisms of the four reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted germylene (HNdouble bond; length as m-dashGeHR) and NaF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the four reactions are 185.0, 208.1, 224.4, and 266.9 kJ/mol, respectively, which are linearly correlated with the calculated barrier heights. Compared with the insertion reaction of HNdouble bond; length as m-dashGe: and R–H, the introduction of NaF makes the insertion reaction occur easily though it is more difficult to proceed than that of insertion reaction between H2GeNaF and R–H. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the four insertion reactions should be as follows: H–F > H–OH > H–NH2 > H–CH3.