Top Organomet Chem (2020) 67: 131–152
https://doi.org/10.1007/3418_2020_50
# Springer Nature Switzerland AG 2020
Published online: 22 July 2020
Computational Modeling of Selected
Photoactivated Processes
Adiran de Aguirre, Victor M. Fernandez-Alvarez, and Feliu Maseras
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
2 Photoredox-Catalyzed Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.1 Dual Ni–Photoredox Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.2 Light-Driven Catalytic Trichloromethylation of Acylpyridines . . . . . . . . . . . . . . . . . . . . . 140
3 Photoactivated Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.1 Photoinduced Oxidative Decarboxylation of a Nonheme Iron(III) Complex . . . . . . . 144
3.2 Light-Driven Insertion of Dioxygen into Pt(II)–C Bonds . . . . . . . . . . . . . . . . . . .. . . . . . . . . 147
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Abstract Photoactivated processes play an increasingly important role in chemistry. Their widespread use is still relatively recent, and the application of computational methods to the treatment of the large systems usually involved in
experimentally relevant systems is even more recent. The application of TD-DFT
calculations for the photoactivation step and of conventional DFT calculations for
selected regions of the potential energy surface has been demonstrated as a powerful
tool for mechanistic understanding. This contribution presents four representative
examples of this application, highlighting the successes and the struggles of this type
of treatments.
Keywords Density functional theory · Iridium · Iron · Nickel · Photocatalysis ·
Photosensitizers · Platinum · Time-dependent density functional theory
A. de Aguirre, V. M. Fernandez-Alvarez, and F. Maseras (*)
Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Catalonia, Spain
e-mail: Adiran-Josu.DeAguirreFondevila@unige.ch; fmaseras@iciq.es
https://doi.org/10.1007/3418_2020_50
# Springer Nature Switzerland AG 2020
Published online: 22 July 2020
Computational Modeling of Selected
Photoactivated Processes
Adiran de Aguirre, Victor M. Fernandez-Alvarez, and Feliu Maseras
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
2 Photoredox-Catalyzed Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.1 Dual Ni–Photoredox Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
2.2 Light-Driven Catalytic Trichloromethylation of Acylpyridines . . . . . . . . . . . . . . . . . . . . . 140
3 Photoactivated Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.1 Photoinduced Oxidative Decarboxylation of a Nonheme Iron(III) Complex . . . . . . . 144
3.2 Light-Driven Insertion of Dioxygen into Pt(II)–C Bonds . . . . . . . . . . . . . . . . . . .. . . . . . . . . 147
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Abstract Photoactivated processes play an increasingly important role in chemistry. Their widespread use is still relatively recent, and the application of computational methods to the treatment of the large systems usually involved in
experimentally relevant systems is even more recent. The application of TD-DFT
calculations for the photoactivation step and of conventional DFT calculations for
selected regions of the potential energy surface has been demonstrated as a powerful
tool for mechanistic understanding. This contribution presents four representative
examples of this application, highlighting the successes and the struggles of this type
of treatments.
Keywords Density functional theory · Iridium · Iron · Nickel · Photocatalysis ·
Photosensitizers · Platinum · Time-dependent density functional theory
A. de Aguirre, V. M. Fernandez-Alvarez, and F. Maseras (*)
Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Catalonia, Spain
e-mail: Adiran-Josu.DeAguirreFondevila@unige.ch; fmaseras@iciq.es