Chapter 5
Mechanistic Insight into the Hydrogen
Activation by Frustrated Lewis Pairs
Mojgan Heshmat, Lei Liu, and Bernd Ensing
Abstract The combination of a Lewis acid (LA) and a Lewis base (LB) in such
a way that they are prevented from forming a classical LA–LB adduct by means
of steric hindrance or thermal hindrance is called a Frustrated Lewis Pair (FLP).
FLPs have been shown to function as metal-free catalysts for small molecule
activation and conversion. In this chapter, we review theoretical results from
combined quantum mechanical calculations and first-principles (DFT) molecular
dynamics/metadynamics simulations with the aim of understanding the mechanistic
aspects of FLP reactivity. Our results are contextualized with the recently published
work from other researchers. The mechanisms of H 2 activation by both inter- and
intramolecular FLPs are examined and the impact of water on FLP reactivity is
discussed. Furthermore, the possibility of alternative mechanisms of H 2 activation
by activated carbonyl carbon is presented. Carbonyl carbon is activated (polarized)
by complexation of the C = O group to a Lewis/Brønsted acid or formation of an Hbond with an H-bond donor in solution. Finally, an overview of applications of Lewis
pair-functionalized metal–organic frameworks (MOFs) for H 2 activation is given.
Keywords Frustrated Lewis pairs · H 2 activation · Homogeneous catalysis ·
Heterogeneous catalysis · DFT calculations · Ab initio molecular dynamics
simulations
M. Heshmat · B. Ensing (B)
Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, 1098 XH Amsterdam,
The Netherlands
e-mail: B.Ensing@uva.nl
M. Heshmat
CAT Catalytic Center, ITMC, RWTH Aachen University, Worringerweg 2, 52074 Aachen,
Germany
L. Liu (B)
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
e-mail: liulei@ipe.ac.cn; liulei3039@gmail.com
© Springer Nature Switzerland AG 2021
J. Chris Slootweg and A. R. Jupp (eds.), Frustrated Lewis Pairs,
Molecular Catalysis 2, https://doi.org/10.1007/978-3-030-58888-5_5
167
Mechanistic Insight into the Hydrogen
Activation by Frustrated Lewis Pairs
Mojgan Heshmat, Lei Liu, and Bernd Ensing
Abstract The combination of a Lewis acid (LA) and a Lewis base (LB) in such
a way that they are prevented from forming a classical LA–LB adduct by means
of steric hindrance or thermal hindrance is called a Frustrated Lewis Pair (FLP).
FLPs have been shown to function as metal-free catalysts for small molecule
activation and conversion. In this chapter, we review theoretical results from
combined quantum mechanical calculations and first-principles (DFT) molecular
dynamics/metadynamics simulations with the aim of understanding the mechanistic
aspects of FLP reactivity. Our results are contextualized with the recently published
work from other researchers. The mechanisms of H 2 activation by both inter- and
intramolecular FLPs are examined and the impact of water on FLP reactivity is
discussed. Furthermore, the possibility of alternative mechanisms of H 2 activation
by activated carbonyl carbon is presented. Carbonyl carbon is activated (polarized)
by complexation of the C = O group to a Lewis/Brønsted acid or formation of an Hbond with an H-bond donor in solution. Finally, an overview of applications of Lewis
pair-functionalized metal–organic frameworks (MOFs) for H 2 activation is given.
Keywords Frustrated Lewis pairs · H 2 activation · Homogeneous catalysis ·
Heterogeneous catalysis · DFT calculations · Ab initio molecular dynamics
simulations
M. Heshmat · B. Ensing (B)
Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, 1098 XH Amsterdam,
The Netherlands
e-mail: B.Ensing@uva.nl
M. Heshmat
CAT Catalytic Center, ITMC, RWTH Aachen University, Worringerweg 2, 52074 Aachen,
Germany
L. Liu (B)
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
e-mail: liulei@ipe.ac.cn; liulei3039@gmail.com
© Springer Nature Switzerland AG 2021
J. Chris Slootweg and A. R. Jupp (eds.), Frustrated Lewis Pairs,
Molecular Catalysis 2, https://doi.org/10.1007/978-3-030-58888-5_5
167