The insertion reactions of the p-complex structure (A) of silylenoid H 2 SiLiF into C-X bonds of CH 3 XH n-1 (X = F, Cl, Br, O, N; n = 1, 1, 1, 2, 3) have been studied using ab initio and DFT methods. The results indicate that the insertions proceed in a concerted manner, forming H 2 SiXH n-1 CH 3 and LiF. The order of reactivity by A insertion indicates the reaction barriers increase for the same-row element X from right to left in the periodic table, whereas change very little for the same-family element X. The insertions of A and the three-membered-ring structure of H 2 SiLiF are similar. Both structures may participate in insertion reactions.
The structures of pentacoordinate silylenoid PhCH 2 (NH 2 )CH 3 SiLiF were studied by density functional theory at the B3LYP/6-31G(d) level. Three equilibrium structures, the three-membered ring (1), the p-complex (2), and the r-complex (3) structures, were located. Their energies are in the order of 2 [ 1 [ 3 both in vacuum and in THF. To exploit the stability of PhCH 2 (NH 2 )CH 3 SiLiF, the insertion reactions of 1 and PhCH 2 (NH 2 )CH 3 Si into C-F have been investigated, respectively. The results show that the insertion of PhCH 2 (NH 2 )CH 3 Si is more favorable. To probe the influence of amine-coordination to the stability of PhCH 2 (NH 2 )CH 3 SiLiF, the insertion reaction of PhCH 3 CH 3 SiLiF was also investigated. The calculations indicate that the insertion of PhCH 3 CH 3 SiLiF is more favorable than that of 1. So the N atom plays an important role on the stability of silylenoid PhCH 2 (NH 2 )CH 3 SiLiF.
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