Cationic Noncovalent Interactions: Energetics and Periodic Trends

Abstract

In this review, noncovalent interactions of ions with neutral molecules are discussed. After defining the scope of the article, which excludes anionic and most protonated systems, methods associated with measuring thermodynamic information for such systems are briefly recounted. An extensive set of tables detailing available thermodynamic information for the noncovalent interactions of metal cations with a host of ligands is provided. Ligands include small molecules (H 2 , NH 3 , CO, CS, H 2 O, CH 3 CN, and others), organic ligands (O-and N-donors, crown ethers and related molecules, MALDI matrix molecules), π-ligands (alkenes, alkynes, benzene, and substituted benzenes), miscellaneous inorganic ligands, and biological systems (amino acids, peptides, sugars, nucleobases, nucleosides, and nucleotides). Hydration of metalated biological systems is also included along with selected proton-based systems: 18-crown-6 polyether with protonated peptides and base-pairing energies of nucleobases. In all cases, the literature thermochemistry is evaluated and, in many cases, reanchored or adjusted to 0 K bond dissociation energies. Trends in these values are discussed and related to a variety of simple molecular concepts.

Coordination chemistry insights into the role of alkali metal promoters in dinitrogen reduction

“…Solvent-cation interactions can promote rearrangement of cations in solution, leading to flexible cation-complex and cation-N 2 interactions. Relevant thermodynamic measurements of alkali cations with O-donor solvents are summarized in Table 2 [61]. These thermodynamic data suggest that Li + forms stronger interactions with O-donor solvents.…”

“…Owing to the electrostatic nature of this interaction, the strength of cation-π interactions increases with increasing z/r (Table 3). Electron-donating substituents on the arene result in stronger cation-π interactions, although this effect is more pronounced for smaller cations [61]. …”

“…The effect of alkali cation sequestration by crown ethers on alkali cation interactions to N 2 will be discussed below. Relevant sequential bond dissociation energies for alkali-crown-ether complexes are listed in Table 4 [61]. …”

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

“…Water-water and water-solute interactions compete and efficiently complement each other in important equilibria [1][2][3][4][5][6][7][8][9].…”

Structural and spectroscopic properties of complexes formed between HNCS and SO 2 in low temperature matrices

“…Weak interactions are important for understanding properties of matter including gas phase, liquid and solid state [1][2][3][4][5][6]. Many physical and chemical processes are governed by non-covalent interactions characterized by binding energy typically less than 80 kJ mol −1 .…”