Título del libro: Chemical Reactivity: Volume 2: Approaches And Applications
Título del capítulo: Predicting reactivity with a general-purpose reactivity indicator
JAMES STEWART MURRAY ANDERSON;
Autores externos:
Idioma:
Año de publicación:
2023
Palabras clave:
Chemical reactivity; Conceptual density functional theory (CDFT); Density functional theory (DFT); Fukui function; General-purpose reactivity indicator; Perturbative perspective model
Resumen:
The reactivity of a site or atom in a molecule is highly transferable and thus largely independent of the reaction partner. The perturbative perspective takes advantage of this observation, and the approach has led us to several useful models for predicting reactivity, particularly one-parameter models. However, one-parameter models are often insufficient to predict the most reactive site or atom in a molecule. This insufficiency led us to the two-parameter model known as the general-purpose reactivity indicator (GPRI) developed from the perturbative perspective that can predict reactivity when different reaction conditions change the reactive atom. In the first part of this chapter, we describe the fundamentals behind the perturbative perspective model to predict the most susceptible atom in a molecule using reactivity indicators such as the electrostatic potential and the condensed Fukui function. Subsequently, we provide some applications to chemical systems by highlighting the perturbative perspective model. In the second part of this chapter, we discuss determining the most reactive site (atom) in a molecule under different reactive conditions. This is the main problem addressed by the GPRI. In this part of the chapter, we describe the derivation of the GPRI model and some applications. Additionally, molecules can have different reactivity depending on the reaction conditions. Hence the GPRI and the corresponding reactivity transition tables are useful in describing the reactivity of molecules in the charge-controlled and the charge-transfer-controlled situations. At the end of this chapter, we share some advice on using these models as well as their strengths and weaknesses. © 2023 Elsevier Inc. All rights reserved.
Entidades citadas de la UNAM:
ISBN:
9780323902595
Editorial:
Elsevier Nombre de la publicación:
Predicting reactivity with a general-purpose reactivity indicator
Página inicial:
159
Página final:
180
