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Predicting novel strong acids of plumbylene at theoretical levels
Author(s) -
Mohebi Nazanin,
Kassaee Mohamad Z.
Publication year - 2021
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4139
Subject(s) - chemistry , protonation , proton affinity , polarizable continuum model , electronegativity , electrophile , homo/lumo , computational chemistry , chloroform , electron affinity (data page) , nucleophile , singlet state , molecular orbital , polarizability , mulliken population analysis , formalism (music) , density functional theory , stereochemistry , molecule , atomic physics , organic chemistry , solvation , physics , ion , musical , visual arts , art , catalysis , excited state
We have reached at new acyclic plumbylenes which show high acidity, via B3LYP, Def2‐TZVP, MP2, and wB97XD functionals. Our scrutinized plumbylenes include dicyclopropaplumbylene ( 1 ), dicyclopentaplumbylene ( 2 ), dicycloheptaplumbylene ( 3 ), and their unsaturated analogs ( 1 ’ ‐ 3 ’ , respectively). All scrutinized plumbylenes and their corresponding protonated forms, 1 H ( 1 ’ H )‐ 3 H ( 3 ’ H ), appear as minima on their energy surfaces. The conductor‐like polarizable continuum model (CPCM) and integral equation formalism polarized continuum model (IEFPCM) are used to predict the p k a values for electrophilic plumbylenes, 1 ( 1 ’ )‐ 3 ( 3 ’ ), in chloroform and water. In most cases, plumbylenes turn out as strong acids for showing relatively high negative p k a values. The acidity trend of plumbylenes (p k a ) appears consistent with their proton affinity (PA), electrophilicity ( ω ), nucleophilicity ( N ), Mulliken electronegativity ( X ), absolute chemical hardness ( η abs ), singlet‐triplet energy gap (ΔE s‐t ), and highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap (ΔE H‐L ). Structure 1 , with two cyclopropyl groups, turns out as the most acidic specie in chloroform and water.