Preface
The use of computational methods to analyze chemical reactivity in general, and
organometallic-based catalysis in particular, has become a common practice among
all the chemists working in the field. Nowadays, most PhD students have contact
with theoretical calculations during their thesis, by collaborating with computational
groups or commonly by performing their own calculations. Thus, theoretical calculations are a tool fully incorporated into the toolkit that a general chemist has
available in the lab.
This book intends to go further than routine DFT calculations of energy profiles
to cover the new directions that computational chemistry is developing to advance
the field of homogeneous and organometallic-based catalysis. To this aim, every
chapter was commissioned to cover each of the specific aspects where modern
computational chemistry is directing its efforts in the organometallic field.
Chapter “What Makes a Good (Computed) Energy Profile?” is intended to give a
critical overview on the general methods employed to compute energy profiles for
mechanistic analysis. It includes a critical description of the main issues a “modeler”
must take into consideration to obtain reliable information on reaction mechanisms.
Chapter “Mechanisms of Metal-Catalyzed Electrophilic F/CF 3 /SCF 3 Transfer
Reactions from Quantum Chemical Calculations” by Prof. Himo covers the computational analysis of reaction mechanisms to a particular process, specifically the F/
CF 3 /SCF 3 transfer reaction, as a representative example on the use of theoretical
methods to investigate reaction mechanisms.
The characterization of energy profiles, however, is on the way to become a fully
automated process. In addition, the automated reaction path search methods allow
the exploration of the full PES without a prejudgment of the products as well as the
reaction paths. Among them, one of the most successful methods is the artificial
force-induced reaction (AFIR) method. Chapter “Artificial Force Induced Reaction
Method for Systematic Elucidation of Mechanism and Selectivity in Organometallic
Reactions,” by Profs. Miho and Maeda describes the AFIR method including
examples of application to organometallic reactions.
Computational studies of organometallic reactions have focused traditionally on
the calculation of Gibbs energy profiles, but experiments focus on reaction rates,
v
The use of computational methods to analyze chemical reactivity in general, and
organometallic-based catalysis in particular, has become a common practice among
all the chemists working in the field. Nowadays, most PhD students have contact
with theoretical calculations during their thesis, by collaborating with computational
groups or commonly by performing their own calculations. Thus, theoretical calculations are a tool fully incorporated into the toolkit that a general chemist has
available in the lab.
This book intends to go further than routine DFT calculations of energy profiles
to cover the new directions that computational chemistry is developing to advance
the field of homogeneous and organometallic-based catalysis. To this aim, every
chapter was commissioned to cover each of the specific aspects where modern
computational chemistry is directing its efforts in the organometallic field.
Chapter “What Makes a Good (Computed) Energy Profile?” is intended to give a
critical overview on the general methods employed to compute energy profiles for
mechanistic analysis. It includes a critical description of the main issues a “modeler”
must take into consideration to obtain reliable information on reaction mechanisms.
Chapter “Mechanisms of Metal-Catalyzed Electrophilic F/CF 3 /SCF 3 Transfer
Reactions from Quantum Chemical Calculations” by Prof. Himo covers the computational analysis of reaction mechanisms to a particular process, specifically the F/
CF 3 /SCF 3 transfer reaction, as a representative example on the use of theoretical
methods to investigate reaction mechanisms.
The characterization of energy profiles, however, is on the way to become a fully
automated process. In addition, the automated reaction path search methods allow
the exploration of the full PES without a prejudgment of the products as well as the
reaction paths. Among them, one of the most successful methods is the artificial
force-induced reaction (AFIR) method. Chapter “Artificial Force Induced Reaction
Method for Systematic Elucidation of Mechanism and Selectivity in Organometallic
Reactions,” by Profs. Miho and Maeda describes the AFIR method including
examples of application to organometallic reactions.
Computational studies of organometallic reactions have focused traditionally on
the calculation of Gibbs energy profiles, but experiments focus on reaction rates,
v