Applications of Computational
Chemistry to Selected Problems
of Transition-Metal Catalysis
in Biological and Nonbiological Systems
Hajime Hirao
Abstract The chemistry of transition-metal-containing systems is highly complex
and diverse and thus lends itself to careful computational investigation. Indeed, computational chemistry can play fundamentally important roles in elucidating the catalytic mechanisms of such systems, by offering information about short-lived intermediates and transition states as well as factors that determine catalytic properties,
which is not easily attained by experimental means. A quantum mechanical description of a targeted catalytic system could be difficult or unfeasible in many circumstances, especially when large systems such as metalloenzymes and coordination
polymers are studied. Nevertheless, valuable insights can still be gained from hybrid
computational techniques that allow concrete realizations of extensive reaction pathway analyses. This chapter gives a brief overview of some of our recent attempts
to study the structure and activity of transition-metal-containing systems varying in
size using several computational approaches.
1 Introduction
The catalytic roles of transition metals in a broad range of chemical and biological
processes have attracted the interest of many researchers over the past decades. Many
attempts have been made to understand the factors that underlie the catalytic properties of transition-metal complexes. However, numerous variations exist in ligands
used to form complexes and oxidation and spin states of transition metals, giving
rise to diverse reactivity patterns that may not easily be generalized. In addition,
ligands often play noninnocent roles in catalysis by getting oxidized or reduced,
thereby adding complexity to the problem. We believe that computational chemistry
has many useful roles to play in teasing out catalytic mechanisms of such systems.
H. Hirao (B)
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue,
Kowloon, Hong Kong, China
e-mail: hhirao@cityu.edu.hk
© 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_15
463
Chemistry to Selected Problems
of Transition-Metal Catalysis
in Biological and Nonbiological Systems
Hajime Hirao
Abstract The chemistry of transition-metal-containing systems is highly complex
and diverse and thus lends itself to careful computational investigation. Indeed, computational chemistry can play fundamentally important roles in elucidating the catalytic mechanisms of such systems, by offering information about short-lived intermediates and transition states as well as factors that determine catalytic properties,
which is not easily attained by experimental means. A quantum mechanical description of a targeted catalytic system could be difficult or unfeasible in many circumstances, especially when large systems such as metalloenzymes and coordination
polymers are studied. Nevertheless, valuable insights can still be gained from hybrid
computational techniques that allow concrete realizations of extensive reaction pathway analyses. This chapter gives a brief overview of some of our recent attempts
to study the structure and activity of transition-metal-containing systems varying in
size using several computational approaches.
1 Introduction
The catalytic roles of transition metals in a broad range of chemical and biological
processes have attracted the interest of many researchers over the past decades. Many
attempts have been made to understand the factors that underlie the catalytic properties of transition-metal complexes. However, numerous variations exist in ligands
used to form complexes and oxidation and spin states of transition metals, giving
rise to diverse reactivity patterns that may not easily be generalized. In addition,
ligands often play noninnocent roles in catalysis by getting oxidized or reduced,
thereby adding complexity to the problem. We believe that computational chemistry
has many useful roles to play in teasing out catalytic mechanisms of such systems.
H. Hirao (B)
Department of Chemistry, City University of Hong Kong, Tat Chee Avenue,
Kowloon, Hong Kong, China
e-mail: hhirao@cityu.edu.hk
© 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_15
463