A B3LYP and MP2(full) theoretical investigation on the cooperativity effect between hydrogen-bonding and cation-molecule interactions and thermodynamic property in the 1: 2 (Na+: N-(Hydroxymethyl)acetamide) ternary complex

Abstract

The cooperativity effects between the O/N-H∙∙∙O hydrogen-bonding and Na⁺∙∙∙O cation-molecule interactions in the 1: 2 (Na⁺: N-(Hydroxymethyl)acetamide) systems were investigated at the B3LYP/6-311++G**, MP2(full)/6-311++G** and MP2(full)/aug-cc-pvtz levels. The thermodynamic cooperativity calculations were also carried out for two pathways of the ternary-complex formation. The result shows that, in most ternary complexes, the O/N-H∙∙∙O and Na⁺∙∙∙O interactions are weakened in comparison with those in binary systems, leading to the anti-cooperativity effects, in particular in the complexes in which only the Na⁺∙∙∙O interactions exist. Shifts of electron density confirm the existence of anti-cooperativity. The increase of favorable enthalpic contribution leads to the positive cooperativity effect with negative ΔG(coop.) on forming the ternary complex by initial N-(Hydroxymethyl)acetamide dimer followed by addition of Na⁺. In forming the ternary complex by Na⁺∙∙∙N-(Hydroxymethyl)acetamide with the second N-(Hydroxymethyl)acetamide unit, the large unfavorable entropy change leads to the negative cooperativity effect with positive ΔG(coop.). The ternary complex is more easily formed by the pathway in which Na⁺ binds to N-(Hydroxymethyl)acetamide dimer.

Cooperativity in Noncovalent Interactions

“…Cation−π interactions are arguably the strongest among noncovalent interactions and have been shown to be modulated by several factors. − ,,,,− A number of experimental and theoretical studies which elucidate cation-induced cooperativity have also emerged. ,− Our group has investigated the fundamental question of how a pair of noncovalent interactions mutually impact each other, especially when one of them is a cation−π interaction. In this regard, two scenarios were studied systematically.…”