Top Organomet Chem (2021) 68: 95–134
https://doi.org/10.1007/3418_2020_65
# Springer Nature Switzerland AG 2020
Published online: 25 December 2020
Cooperative Reactivity by Pincer-Type
Complexes Possessing Secondary
Coordination Sphere
Ajeet Singh, Evamarie Hey-Hawkins, and Dmitri Gelman
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
1.1 Genesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2 Carbometalated Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1 C(sp
2
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.2 C(sp
3
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3 N-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3.1 N(sp
2
)-Based Pincer Complexes Possessing Lewis Acid Functionalities . . . . . . . . . . . 113
3.2 N(sp
2
)-Based Pincer Complexes Possessing Hydrogen Bonding Functionalities . . . 120
3.3 Binuclear Reactivity of N(sp
2
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Abstract Pincer complexes represent a family of potent compounds having a
tremendous number of manifold applications in organometallic chemistry, synthesis,
catalysis, materials science, and bioinorganic chemistry. This chapter overviews the
recent developments in the chemistry and catalytic applications of pincer complexes
incorporating secondary coordination sphere or an appended functionality that can
interact with the catalytic center or can modulate its reactivity via secondary
substrate-catalyst interactions. Combining the concepts of modular and stable pincer
A. Singh
Institute of Chemistry, The Hebrew University, Jerusalem, Israel
E. Hey-Hawkins (*)
Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University,
Leipzig, Germany
e-mail: hey@uni-leipzig.de
D. Gelman (*)
Institute of Chemistry, The Hebrew University, Jerusalem, Israel
Peoples’ Friendship University of Russia (RUDN University), Moscow, Russia
e-mail: dmitri.gelman@mail.huji.ac.il
https://doi.org/10.1007/3418_2020_65
# Springer Nature Switzerland AG 2020
Published online: 25 December 2020
Cooperative Reactivity by Pincer-Type
Complexes Possessing Secondary
Coordination Sphere
Ajeet Singh, Evamarie Hey-Hawkins, and Dmitri Gelman
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
1.1 Genesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2 Carbometalated Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1 C(sp
2
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.2 C(sp
3
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3 N-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
3.1 N(sp
2
)-Based Pincer Complexes Possessing Lewis Acid Functionalities . . . . . . . . . . . 113
3.2 N(sp
2
)-Based Pincer Complexes Possessing Hydrogen Bonding Functionalities . . . 120
3.3 Binuclear Reactivity of N(sp
2
)-Based Pincer Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
Abstract Pincer complexes represent a family of potent compounds having a
tremendous number of manifold applications in organometallic chemistry, synthesis,
catalysis, materials science, and bioinorganic chemistry. This chapter overviews the
recent developments in the chemistry and catalytic applications of pincer complexes
incorporating secondary coordination sphere or an appended functionality that can
interact with the catalytic center or can modulate its reactivity via secondary
substrate-catalyst interactions. Combining the concepts of modular and stable pincer
A. Singh
Institute of Chemistry, The Hebrew University, Jerusalem, Israel
E. Hey-Hawkins (*)
Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University,
Leipzig, Germany
e-mail: hey@uni-leipzig.de
D. Gelman (*)
Institute of Chemistry, The Hebrew University, Jerusalem, Israel
Peoples’ Friendship University of Russia (RUDN University), Moscow, Russia
e-mail: dmitri.gelman@mail.huji.ac.il