Exploring the Relationship between Reactivity and Electronic Structure in Isorhodanine Derivatives Using Computer Simulations

Abstract

The electronic structure and reactivity of 22 isorhodanine (IsRd) derivatives in the Diels–Alder reaction with dimethyl maleate (DMm) were investigated under two different environments (gas phase and continuous solvent CH3COOH), using free Gibbs activation energy, free Gibbs reaction energy, and frontier molecular orbitals to analyze their reactivity. The results revealed both inverse electronic demand (IED) and normal electronic demand (NED) characteristics in the Diels–Alder reaction and also provided insights into the aromaticity of the IsRd ring by employing HOMA values. Additionally, the electronic structure of the IsRd core was analyzed through topological examination of the electron density and electron localization function (ELF). Specifically, the study demonstrated that ELF was able to successfully capture chemical reactivity, highlighting the potential of this method to provide valuable insights into the electronic structure and reactivity of molecules.

Evolution of the Electronic Structure of the trans-[Re6S8bipy4Cl2] Octahedral Rhenium Cluster during Reduction

“…It was also shown that the interaction energy between the cluster core and bipy ligands correlates linearly with the population of the V(Re, N in ) ELF basin. The behavior, when the basin population correlates with some bond related properties, is intuitive but does not have much confirmation in the literature [51][52][53]. Finally, since other members of the [Re 6 Q 8 L 4 X 2 ] (Q=S or Se; X=Cl or Br; L = 4,4 -bipyridine, 4-phenylpyridine) cluster family have a similar electronic structure to [Re 6 S 8 bipy 4 Cl 2 ], tendencies made in the current work can most likely also be applied to these compounds.…”