DFT-B3LYP study of interactions between host biphenyl-1-aza-18-crown-6 ether derivatives and guest Cd2+: NBO, NEDA, and QTAIM analyses

Abstract

This report present the results of natural energy decomposition analysis (NEDA), natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM) calculations of three derivatives of biphenyl-1-aza-18-crown-6 ether and their 1:1 complexes with Cd(2+). All calculations used the B3LYP density functional theory in combination with the 6-311G and WTBS basis sets for ligands and Cd(2+) ion, respectively. Ligands 1 and 3 have a single 1-aza-18-crown-6, substituent; ligand 2 has two such substituents. The results show that, in the optimized geometries of the complexes, the distance between N and Cd(2+) is greater than the distance between O and Cd(2+). NBO and QTAIM data confirm these results. There was no stabilization energy or bond critical point for N · · · Cd(2+) in NBO or QTAIM, respectively. Data show that the O · · · Cd(2+) interaction is a kind of closed shell interaction. The trend of the calculated stabilization energy was similar to the experimental data. Different contributions of interaction energies for complex formation were analyzed by NEDA, and the results show that the main component of the interactions is accounted for by polarization.

Synthesis, structure and theoretical simulation of a zinc(II) coordination complex with 2,3-pyridinedicarboxylate

“…This is in agreement with previous conclusions on the subject [32]. Moreover, we found from the NBO analysis that electronic delocalizations from LP(Zn) and LP*(Zn) to some RY* of the oxygen and nitrogen atoms occur although with lower energies, where RY* designates the 1-center Rydberg non-Lewis NBOs.…”

Acidity enhancement of α‐carbon of beta diketones via hydroxyl substituents: A density functional theory study

“…For each donor orbital (i.e., lone pair electrons of oxygen) and acceptor orbital ( j : σ* O–H ), the stabilization energy E (2) associated with i → j delocalization is given by the following equation: where ε i and ε j are NBO orbital energies and F is the Fock operator. [ 17–20 ] The stabilization energy ( E (2)) values for the structures of hydroxyl derivatives of beta diketones and their corresponding conjugate bases are given in Tables 3 and 4, respectively, which are estimated from the NBO analysis of the structures optimized at B3LYP/6311++G(d,p) level of theory. Also, the amount of charge transfer between donor and acceptor orbitals can be obtained using Equations and .…”

Gold(I)-Initiated Cycloisomerization/Diels–Alder/Retro-Diels–Alder Cascade Strategy to Biaryls

“…Biaryls are important scaffolds in a wide range of natural products, pharmaceutically active molecules, chiral ligands, crown ethers, and liquid crystals . Due to the increasing demand for efficient strategies for constructing biaryl compounds, a number of methodologies have been developed, in which the transition-metal-catalyzed cross-coupling reactions were the predominant methods. ,, Moreover, a strategy to synthesize biaryls by the construction of one aryl ring via transition-metal-catalyzed [2+2+2] cycloaddition of alkynes or Diels–Alder cycloaddition/aromatization also drew considerable attention. ,, Also, some gold-catalyzed approaches to biaryls have been reported …”