A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry
This chapter presents the combination of the activation strain model (ASM) of reactivity and the energy decomposition analysis (EDA) methods as an alternative approach to gain quantitative insight into the reactivity trends in organometallic chemistry. Be
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A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry Israel Fernández
Contents 1 Introduction 2 The Activation Strain Model of Reactivity and Energy Decomposition Analysis Methods 3 Representative Applications of the ASM and EDA-NOCV Methods 3.1 Diels–Alder Cycloaddition Reaction Involving Metallaanthracenes 3.2 Oxidative Addition Reactions 3.3 Gold Complexes in π-Acid Catalysis: Hydroamination and Hydroarylation 3.4 Intramolecular Reactions: β-Cl vs β-H Elimination 4 Summary and Outlook References
Abstract This chapter presents the combination of the activation strain model (ASM) of reactivity and the energy decomposition analysis (EDA) methods as an alternative approach to gain quantitative insight into the reactivity trends in organometallic chemistry. Besides a brief presentation of the basics of these quantum chemical methods, representative recent applications of this approach to fundamental transition metal (TM)-mediated reactions are discussed. The selected transformations span from typical oxidative addition or β-elimination processes to more intricate gold (I)-mediated hydroarylation or hydroamination reactions, therefore covering a good number of different processes in organometallic chemistry. The contents of this chapter show not only the good performance of this computational methodology to understand the physical factors controlling the reactivity in organometallic chemistry but also its usefulness toward the rational design of more efficient transformations.
I. Fernández (*) Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Madrid, Spain e-mail: [email protected]
I. Fernández
Keywords Activation strain model · DFT calculations · Energy decomposition analysis · Reactivity
Abbreviations ASM DFT EDA NOCV
Activation strain model Density functional theory Energy decomposition analysis 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 whic
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