A computational study to determine whether substituents make E13 [[triple bond, length as m-dash]] nitrogen (E13 = B, Al, Ga, In, and Tl) triple bonds synthetically accessible

摘要

This study theoretically determines the effect of substituents on the stability of the triple-bonded L–E _(13) N–L (E _(13) = B, Al, Ga, In, and Tl) compound using the M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp levels of theory. Five small substituents (F, OH, H, CH _(3) and SiH _(3) ) and four large substituents (SiMe(Si t Bu _(3) ) _(2) , Si i PrDis _(2) , Tbt ( C _(6) H _(2) -2,4,6-{CH(SiMe _(3) ) _(2) } _(3) ) and Ar* (C _(6) H _(3) -2,6-(C _(6) H _(2) -2,4,6-i-Pr _(3) ) _(2) )) are used. Unlike other triply bonded L–E _(13) P–L, L–E _(13) As–L, L–E _(13) Sb–L and L–E _(13) Bi–L molecules that have been studied, the theoretical findings for this study show that both small (but electropositive) ligands and bulky substituents can effectively stabilize the central E _(13) N triple bond. Nevertheless, these theoretical observations using the natural bond orbital and the natural resonance theory show that the central E _(13) N triple bond in these acetylene analogues must be weak, since these E _(13) N compounds with various ligands do not have a real triple bond.