Theoretical Study on the Regioselectivity of Leapfrog B18 and B30 Boron Sheets in Electrophilic and Nucleophilic Reactions Using DFT-Based Reactivity Indices
Auteur(s): Jules Tshishimbi MuyaNom de la revue/Journal: The Journal of Physical Chemistry A
Volume: 128
Numéro: 12
Année: 2024
pages: 2295-2305
Résumé
<p><span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">A combined computational and interpretational DFT study is performed to investigate the regioselectivity of B</span>18<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> and B</span>30<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> leapfrog boron sheets upon reaction with XH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">-type electrophiles and nucleophiles (X = N, P, As, B, Al). The M062X, B3LYP, and B3LYP-D3 functionals are used combined with the 6–31+G(d,p) basis. The molecular electrostatic potential (MEP), Fukui functions, and the dual descriptor are employed to predict the local reactivity of B</span>18<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> and B</span>30<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">. Our results reveal that both clusters are hard and prefer to react with hard bases and acids, such as NH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> and BH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">. Further, these leapfrog B</span>6n<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> clusters can play the role of catalysts as they break B–H and Al–H bonds of BH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> and AlH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> in </span><i>s</i><span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">-BH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">–B</span>6n<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> and </span><i>s</i><span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">-AlH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">–B</span>6<i>n</i><span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> complexes, respectively. Leapfrog B</span>6<i>n</i><span style="background-color:rgb(255,255,255);color:rgb(34,34,34);">–XH</span>3<span style="background-color:rgb(255,255,255);color:rgb(34,34,34);"> complexes (X = B and Al) can be considered as an interaction between two electron-deficient systems. Therefore, the chemical reactivity between …</span></p>