Mechanism and Kinetics
in Homogeneous Catalysis:
A Computational Viewpoint
Jeremy N. Harvey
Abstract The use of computational methods based on electronic structure theory
and statistical mechanics to study reaction mechanisms and kinetics in homogeneous
catalysis, especially organometallic catalysis and organocatalysis, is reviewed. The
chapter focuses mostly on examples from the authors’ own group, published over
the last two decades, and discusses progress and remaining challenges. It is argued
that while it plays a valuable role in mechanistic studies, computation is not yet able
to replace experimental studies.
1 Introduction
Quantum chemical methods play an ever-greater role in investigating chemical reaction mechanisms. In this chapter, I will discuss some important aspects associated
with this type of modeling, with a specific focus on organic and organometallic
chemistry, including homogeneous catalytic reactions. This is an area in which my
group has been working essentially since the beginning of my independent research
career, yet unlike for some other fields in which we have worked, I have not previously written any reviews on this topic. As well as drawing on examples of our own
work from various periods, I will also discuss work from other groups and attempt
to address what I feel are some of the main challenges to this type of work at the
current time. Of necessity, this will also require looking back at how well various
studies carried out previously have stood up to the test of time.
J. N. Harvey (B)
Department of Chemistry and Division of Quantum Chemistry and Physical Chemistry, KU
Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
e-mail: Jeremy.harvey@kuleuven.be
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_10
289
in Homogeneous Catalysis:
A Computational Viewpoint
Jeremy N. Harvey
Abstract The use of computational methods based on electronic structure theory
and statistical mechanics to study reaction mechanisms and kinetics in homogeneous
catalysis, especially organometallic catalysis and organocatalysis, is reviewed. The
chapter focuses mostly on examples from the authors’ own group, published over
the last two decades, and discusses progress and remaining challenges. It is argued
that while it plays a valuable role in mechanistic studies, computation is not yet able
to replace experimental studies.
1 Introduction
Quantum chemical methods play an ever-greater role in investigating chemical reaction mechanisms. In this chapter, I will discuss some important aspects associated
with this type of modeling, with a specific focus on organic and organometallic
chemistry, including homogeneous catalytic reactions. This is an area in which my
group has been working essentially since the beginning of my independent research
career, yet unlike for some other fields in which we have worked, I have not previously written any reviews on this topic. As well as drawing on examples of our own
work from various periods, I will also discuss work from other groups and attempt
to address what I feel are some of the main challenges to this type of work at the
current time. Of necessity, this will also require looking back at how well various
studies carried out previously have stood up to the test of time.
J. N. Harvey (B)
Department of Chemistry and Division of Quantum Chemistry and Physical Chemistry, KU
Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
e-mail: Jeremy.harvey@kuleuven.be
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_10
289