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An Orbital‐Overlap Complement to Atomic Partial Charge
Author(s) -
Mehmood Arshad,
Janesko Benjamin G.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201702715
Subject(s) - partial charge , chemistry , partial oxidation , computational chemistry , atom (system on chip) , chemical physics , cyclobutadiene , nucleophile , charge (physics) , molecule , physics , organic chemistry , quantum mechanics , oxygen , computer science , embedded system , catalysis
Atomic partial charges are widely used to predict reactivity. Partial charge alone is often insufficient: the carbons of benzene and cyclobutadiene, or those of diamond, graphene, and C 60 , possess nearly identical partial charges and very different reactivities. Our atomic overlap distance complements computed partial charges by measuring the size of orbital lobes that best overlap with the wavefunction around an atom. Compact, chemically stable atoms tend to have overlap distances smaller than chemically soft, unstable atoms. We show here how combining atomic charges and overlap distances captures trends in aromaticity, nucleophilicity, allotrope stability, and substituent effects. Applications to recent experiments in organic chemistry (counterintuitive Lewis base stabilization of alkenyl anions in anionic cyclization) and nanomaterials chemistry (facile doping of the central atom in Au 7 hexagons) illustrate this combination's predictive power.