Top Organomet Chem (2020) 67: 107–130
https://doi.org/10.1007/3418_2020_43
# Springer Nature Switzerland AG 2020
Published online: 15 May 2020
A Quantitative Approach to Understanding
Reactivity in Organometallic Chemistry
Israel Fernández
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2 The Activation Strain Model of Reactivity and Energy Decomposition Analysis
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3 Representative Applications of the ASM and EDA-NOCV Methods . . . . . . . . . . . . . . . . . . . . . 111
3.1 Diels–Alder Cycloaddition Reaction Involving Metallaanthracenes . . . . . . . . . . . . . . . . 111
3.2 Oxidative Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.3 Gold Complexes in π-Acid Catalysis: Hydroamination and Hydroarylation . . . . . . . . 117
3.4 Intramolecular Reactions: β-Cl vs β-H Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
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: israel@quim.ucm.es
https://doi.org/10.1007/3418_2020_43
# Springer Nature Switzerland AG 2020
Published online: 15 May 2020
A Quantitative Approach to Understanding
Reactivity in Organometallic Chemistry
Israel Fernández
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2 The Activation Strain Model of Reactivity and Energy Decomposition Analysis
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3 Representative Applications of the ASM and EDA-NOCV Methods . . . . . . . . . . . . . . . . . . . . . 111
3.1 Diels–Alder Cycloaddition Reaction Involving Metallaanthracenes . . . . . . . . . . . . . . . . 111
3.2 Oxidative Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.3 Gold Complexes in π-Acid Catalysis: Hydroamination and Hydroarylation . . . . . . . . 117
3.4 Intramolecular Reactions: β-Cl vs β-H Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
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: israel@quim.ucm.es