The N-atom in [N(PR₃)₂]⁺ cations (R = Ph, Me) can act as electron donor for (pseudo) anti-electrostatic interactions

Abstract

A CSD analysis and DFT study reveal that the nitrogen lone-pair in ijNIJPPh 3 ) 2 ] + is partially intact and involved in intramolecular hydrogen bonding. Computations with the model cation ijNIJPMe 3 ) 2 ] + indicate that intermolecular hydrogen bonding with this ion's N-atom is possible (−8.3 kcal mol −1 for H 2 O as hydrogen bond donor), presenting a rare example of pseudo anti electrostatic hydrogen bonding.

Can Counter‐Intuitive Halogen Bonding Be Coulombic?

“…[58][59][60] The interactions that we label counter-intuitive have sometimes been called "anti-electrostatic." [30,32,35] We believe that this is misleading; it implies that the alternative is "electrostatic," which is incorrect because electrostatics never operates alone. As discussed in section 2, any electrostatic potential is always and necessarily accompanied by a polarizing electric field [eq.…”

“…Attractive interactions between positive σ‐ or π‐hole potentials and negative sites are well known [6–12] and not surprising; they. can be described as “intuitive.” However there can also be “counter‐intuitive” interactions, [27–35] in which the σ‐ or π‐hole potential and the site with which it interacts have the same sign, positive or negative, in the ground‐state molecules.…”

“…can be described as "intuitive." However there can also be "counter-intuitive" interactions, [27][28][29][30][31][32][33][34][35] in which the σor π-hole potential and the site with which it interacts have the same sign, positive or negative, in the ground-state molecules.…”

NO3− anions can act as Lewis acid in the solid state

“…1b,c ). We wondered to what extend this rationale applies to nitrate anions and if perhaps this anion might function as a π-hole to enable so-called (pseudo)anti-electrostatic interactions 13 14 . This seems counterintuitive, yet the charge distribution in naked NO 3 − is anisotropic and reminiscent of a π-hole ( Fig.…”

Bis(phosphangulene)iminium Salts. Holding on to Fullerenes with Phangs

“…S a l t s o f t h e a n a l o g o u s b i s -(triphenylphosphine)iminium cation ([(Ph 3 P) 2 N] + ) were first reported in 1961, 23 and over 1000 structures have since been described. 24,25 Salts of [(Ph 3 P) 2 N] + have special properties attributed to the large globular shape and aromatic surface of the cation. 24−30 These features help make the [(Ph 3 P) 2 N] + ion weakly coordinating and enhance the solubility of its salts in organic solvents, facilitate crystallization, and stabilize reactive anions.…”