Top Organomet Chem (2021) 68: 1–24
https://doi.org/10.1007/3418_2020_67
# Springer Nature Switzerland AG 2020
Published online: 24 December 2020
Recent Advances in the Applications
of Metal-Ligand Cooperation via
Dearomatization and Aromatization
of Pincer Complexes
Amit Kumar and David Milstein
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Metal-Ligand Cooperation for CO 2 Activation and for the Benzene Carbonylation . . . . . . . 4
3 Catalytic Transformation of N 2 O via Metal-Ligand Cooperation . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4 Template Catalysis via Metal-Ligand Cooperation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Abstract Metal-ligand cooperation (MLC) has played an important role in the
development of new green homogeneous catalytic reactions. In the past we have
discovered a new mode of MLC which is based on the dearomatization and
aromatization of pincer complexes and have utilized it to uncover new modes of
bond activation and new catalytic reactions that are atom-economic, environmentally benign and sustainable. Building upon our earlier discoveries which have been
well-reviewed in the past, this chapter discusses recent progresses on the application
of the concept of MLC via dearomatization and aromatization of pincer complexes.
Bond activation of greenhouse gases such as CO 2 and N 2 O and their applications in
the development of catalytic reactions have been discussed in detail. Additionally,
the new concept of template catalysis where catalytic transformation occurs mainly
on the pincer ligand and the metal centre acts as an “anchor” has also been discussed.
Template catalysis utilizes the tool of MLC via dearomatization/aromatization to
A. Kumar
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel
School of Chemistry, University of St. Andrews, St. Andrews, UK
D. Milstein (*)
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel
e-mail: david.milstein@weizmann.ac.il
https://doi.org/10.1007/3418_2020_67
# Springer Nature Switzerland AG 2020
Published online: 24 December 2020
Recent Advances in the Applications
of Metal-Ligand Cooperation via
Dearomatization and Aromatization
of Pincer Complexes
Amit Kumar and David Milstein
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2 Metal-Ligand Cooperation for CO 2 Activation and for the Benzene Carbonylation . . . . . . . 4
3 Catalytic Transformation of N 2 O via Metal-Ligand Cooperation . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4 Template Catalysis via Metal-Ligand Cooperation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5 Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Abstract Metal-ligand cooperation (MLC) has played an important role in the
development of new green homogeneous catalytic reactions. In the past we have
discovered a new mode of MLC which is based on the dearomatization and
aromatization of pincer complexes and have utilized it to uncover new modes of
bond activation and new catalytic reactions that are atom-economic, environmentally benign and sustainable. Building upon our earlier discoveries which have been
well-reviewed in the past, this chapter discusses recent progresses on the application
of the concept of MLC via dearomatization and aromatization of pincer complexes.
Bond activation of greenhouse gases such as CO 2 and N 2 O and their applications in
the development of catalytic reactions have been discussed in detail. Additionally,
the new concept of template catalysis where catalytic transformation occurs mainly
on the pincer ligand and the metal centre acts as an “anchor” has also been discussed.
Template catalysis utilizes the tool of MLC via dearomatization/aromatization to
A. Kumar
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel
School of Chemistry, University of St. Andrews, St. Andrews, UK
D. Milstein (*)
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel
e-mail: david.milstein@weizmann.ac.il