Triple Bonds between Bismuth and Group 13 Elements: Theoretical Designs and Characterization

Abstract

The effect of substitution on the potential energy surfaces of RE 13 ≡BiR (E

A computational study to determine whether substituents make E13nitrogen (E13 = B, Al, Ga, In, and Tl) triple bonds synthetically accessible

“…Although the authors have already published 14 papers concerning group 13 group 15 triple bond molecules, [52][53][54][55][56][57][58][59][60][61][62][63][64][65] the present computational evidence demonstrates that the results about the stability of the triply bonded RE 13 ^NR compounds are quite different from our previous theoretical examinations. For instance, the theoretical conclusions based on our previous papers show that only the bulky ligands can stabilize the triply bonded L-E 13 ^E15 -L (E 15 ¼ P, As, Sb, and Bi) molecules.…”

“…Interestingly, unlike the other L-E 13 ^E15 -L molecular systems that have been previously studied, [50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] the theoretical data for this study using three DFT methods suggest that when ligands are small and electropositive, the triply bonded L-B^N-L molecule could be experimentally produced and detected, since these triple bonded species are more thermodynamically stable than their corresponding doubly bonded L 2 B]N: and :B]NR 2 isomers. Actually, these triply bonded L-B^N-L species, which is isoelectronic to the alkynes L-C^C-L and which contain small and electropositive substituents were experimentally isolated and structurally characterized about three decades ago.…”

“…In order to determine the valence electronic structures of L-E 13 ^N-L, similarly to our previous studies, [50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] the L-E 13 ^N-L species is divided into two fragments: L-E 13 and L-N. These are shown in Fig.…”

“…For instance, the theoretical conclusions based on our previous papers show that only the bulky ligands can stabilize the triply bonded L-E 13 ^E15 -L (E 15 ¼ P, As, Sb, and Bi) molecules. [52][53][54][55][56][57][58][59][60][61][62][63][64][65] Nevertheless, in this work, the authors' computations in this work reveal that both small (but electropositive) ligands and bulky substituents can effectively stabilize the triply bonded L-E 13 ^N-L compounds. In other words, the present theoretical evidences emphasize that both small (but electropositive) substituents and sterically bulky groups can successfully protect the central triple bond, which, in turn, can increase the bond order of this triple bond.…”

“…Recently, molecules containing a L-E 13 ^E15 -L (E 13 ¼ B, Al, Ga, In, and Tl; E 15 ¼ P, As, Sb, and Bi) triple bond, which are isoelectronic to the alkyne analogues R-E 14 ^E14 -R (E 14 ¼ C, Si, Ge, Sn and Pb), have been the subject of theoretical study. [52][53][54][55][56][57][58][59][60][61][62][63][64][65] This study focuses on the other acetylene analogues; i.e., the triply bonded L-E 13 ^N-L compounds that contain group 13 (E 13 ) and nitrogen atoms. As far as the authors are aware, only very few triply bonded compounds that contain a nitrogen element (i.e., L-B^N-L, [66][67][68][69] L-Ga^N-L, 70,71 and L-In^N-L 70 ) have been successfully synthesized and isolated.…”