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Abstract The PnF2(Pn=P,As,Sb,Bi) on a naphthalene scaffold can engage in an internal pnicogen Pn⋅⋅⋅N bond (PnB) with an NH2group placed close to it on the adjoining ring. An approaching neutral NH3molecule can engage in a second PnB with the central Pn, which tends to weaken the intramolecular bond. The presence of the latter in turn weakens the intermolecular PnB with respect to that formed in its absence. Replacement of the external NH3by a CN−anion causes a fundamental change in the bonding pattern, producing a fourth covalent bond with Pn, which rearranges into a trigonal bipyramidal motif. This addition disrupts the internal Pn⋅⋅⋅N pnicogen bond, recasting the PnF2⋅⋅⋅NH2interaction into an NH⋅⋅⋅F H‐bond.
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Anions as Lewis Acids in Noncovalent Bonds
Abstract The ability of an anion to serve as electron‐accepting Lewis acid in a noncovalent bond is assessed via DFT calculations. NH3is taken as the common base, and is paired with a host of ACln−anions, with central atom A=Ca, Sr, Mg, Te, Sb, Hg, Zn, Ag, Ga, Ti, Sn, I, and B. Each anion reacts through its σ or π‐hole although the electrostatic potential of this hole is quite negative in most cases. Despite the contact between this negative hole and the negative region of the approaching nucleophile, the electrostatic component of the interaction energy of each bond is highly favorable, and accounts for more than half of the total attractive energy. The double negative charge of dianions precludes a stable complex with NH3.
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- Award ID(s):
- 1954310
- PAR ID:
- 10624144
- Publisher / Repository:
- cej
- Date Published:
- Journal Name:
- Chemistry – A European Journal
- ISSN:
- 0947-6539
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1002/chem.202402267
