Keywords Activation strain model · DFT calculations · Energy decomposition
analysis · Reactivity
Abbreviations
ASM
Activation strain model
DFT
Density functional theory
EDA
Energy decomposition analysis
NOCV Natural orbitals for chemical valence
1 Introduction
Organometallic compounds are ubiquitous in practically all fields of chemistry, from
transition metal-mediated organic synthesis to materials science or medicinal chemistry. For this reason, understanding the ultimate factors which govern their reactivity is crucial in order to rationally design new organometallic compounds with
potential applications as catalysts, new materials, or drugs.
In this sense, computational organometallic chemistry has emerged as a really
powerful and valuable tool, particularly in the last decades, as clearly shown in the
different chapters of the present book. This is mainly due to tremendous development of computer science together with the progress made on new theoretical
methods (mainly based on the density functional theory) and computational chemistry software. As a result, it is nowadays relatively easy to compute large systems
having transition metals and/or bulky ligands in their structures.
In this particular book chapter, we shall focus on a relatively recent computational
methodology which is based on the combination of the so-called activation strain
model (ASM) of reactivity and energy decomposition analysis (EDA) methods. This
approach has enormously contributed to our current understanding of fundamental
transformations not only in organic chemistry but also in transition metal-mediated
processes. Herein, we will present the good performance of this combined method to
provide a deeper and quantitative understanding of the reactivity of organometallic
species. To this end, selected representative applications of this approach (mainly
coming from our laboratories) to transition metal-mediated reactions will be
discussed.
2 The Activation Strain Model of Reactivity and Energy
Decomposition Analysis Methods
As the theoretical background and applications of ASM have been reviewed recently
[1–4], herein we shall only briefly describe the basics of this approach.
108
I. Fernández
analysis · Reactivity
Abbreviations
ASM
Activation strain model
DFT
Density functional theory
EDA
Energy decomposition analysis
NOCV Natural orbitals for chemical valence
1 Introduction
Organometallic compounds are ubiquitous in practically all fields of chemistry, from
transition metal-mediated organic synthesis to materials science or medicinal chemistry. For this reason, understanding the ultimate factors which govern their reactivity is crucial in order to rationally design new organometallic compounds with
potential applications as catalysts, new materials, or drugs.
In this sense, computational organometallic chemistry has emerged as a really
powerful and valuable tool, particularly in the last decades, as clearly shown in the
different chapters of the present book. This is mainly due to tremendous development of computer science together with the progress made on new theoretical
methods (mainly based on the density functional theory) and computational chemistry software. As a result, it is nowadays relatively easy to compute large systems
having transition metals and/or bulky ligands in their structures.
In this particular book chapter, we shall focus on a relatively recent computational
methodology which is based on the combination of the so-called activation strain
model (ASM) of reactivity and energy decomposition analysis (EDA) methods. This
approach has enormously contributed to our current understanding of fundamental
transformations not only in organic chemistry but also in transition metal-mediated
processes. Herein, we will present the good performance of this combined method to
provide a deeper and quantitative understanding of the reactivity of organometallic
species. To this end, selected representative applications of this approach (mainly
coming from our laboratories) to transition metal-mediated reactions will be
discussed.
2 The Activation Strain Model of Reactivity and Energy
Decomposition Analysis Methods
As the theoretical background and applications of ASM have been reviewed recently
[1–4], herein we shall only briefly describe the basics of this approach.
108
I. Fernández