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Computational Studies in Organometallic Chemistry

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About this book

The series Structure and Bonding publishes critical Reviews on Topics of Research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.

The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed.

Table of Contents

Frontmatter
Modelling and Rationalizing Organometallic Chemistry with Computation: Where Are We?
Abstract
In this chapter, a perspective on how the field of applied computational organometallic chemistry has developed since the mid-1980s is presented. We describe the way in which the modelling of chemical systems has evolved over time, using metallocene chemistry as an example, and highlight the successes and limitations of simple models that were mandatory in the early days of the discipline. A number of more recent case studies are then presented where the full experimental system is now employed and a more quantitative outcome is sought. This includes examples from the Ce-mediated hydrogenation of pyridine, Rh-catalysed C–H bond activation and functionalization, Pd-catalysed azidocarbonylation and phenyl iodide activation at Ru(II) complexes. We conclude with our take on the title question.
Lionel Perrin, Kevin J. T. Carr, David McKay, Claire L. McMullin, Stuart A. Macgregor, Odile Eisenstein
Reactivities and Electronic Properties of Boryl Ligands
Abstract
Transition metal boryl complexes play an important role as reactive intermediates in many catalytic processes. The reactivities and electronic properties of boryl ligands, in particular their nucleophilic and electrophilic behaviors, are discussed and reviewed in this article.
Zhenyang Lin
QM/MM Calculations on Selectivity in Homogeneous Catalysis
Abstract
The application of QM/MM methods to the study of the reaction mechanisms involved in chemo-, regio-, and enantio- selective processes has been a very productive area of research in the last two decades. This review summarizes basic general ideas in both QM/MM methods and the computational study of selectivity and presents selected results on the study of three of the most representative examples of these applications: rhodium-catalyzed hydrogenation, rhodium-catalyzed hydroformylation, and copper-catalyzed cyclopropanation.
Jesús Jover, Feliu Maseras
Realistic Simulation of Organometallic Reactivity in Solution by Means of First-Principles Molecular Dynamics
Abstract
The application of first-principles molecular dynamics simulations to the study of the reactivity of organometallic complexes is surveyed, with special emphasis on studies addressing catalytic processes. We focused on modeling studies in which the solvent, either water or nonaqueous, is explicitly represented. Where available, comparison is made with results obtained from static calculations based on reduced model systems (clusters). In doing so, we show how the mechanistic insight provided by modeling studies of reactions involving charge separation (e.g., proton release) or unsaturated species may qualitatively and quantitatively change when more extended model systems are considered. General aspects of the methodology are also presented.
Pietro Vidossich, Agustí Lledós, Gregori Ujaque
Computation of Excited States of Transition Metal Complexes
Abstract
In this review we discuss the theory and application of methods of excited state quantum chemistry to excited states of transition metal complexes. We review important works in the field and, in more detail, discuss our own studies of electronic spectroscopy and reactive photochemistry. These include binary metal carbonyl photodissociation and subsequent non-adiabatic relaxation, Jahn–Teller and pseudo-Jahn–Teller effects, photoisomerization of transition metal complexes, and coupled cluster response theory for electronic spectroscopy. We aim to give the general reader an idea of what is possible from modern state-of-the-art computational techniques applied to transition metal systems.
Nuno M. S. Almeida, Russell G. McKinlay, Martin J. Paterson
d10-ML2 Complexes: Structure, Bonding, and Catalytic Activity
Abstract
Our goal in this chapter is to show how one can obtain a better understanding of the decisive factors for the selectivity and efficiency of catalytically active metal complexes. This ongoing research project has been designated the ‘Fragment-oriented Design of Catalysts’ and aims at providing design principles for a more rational development of catalysts. To this end, we have performed a series of studies in which we systematically investigate the effect of a specific variation on the reactivity of the catalyst. Thus, we will summarize previous results on not only how the reaction barrier varies when different bonds are activated by palladium, different ligands are attached to palladium but also how different metal centers perform compared to palladium. In a final section, we present a case study on newly obtained results about the effect of adding substituents with different electronegativity to the phosphine ligands at the metal center. A red thread throughout the chapter, and our methodology in general, is the application of the activation strain model of chemical reactivity. This is a predictive model that provides a quantitative relationship between trends in barrier heights and variation of geometric and electronic properties of the reactants.
Lando P. Wolters, F. Matthias Bickelhaupt
The Electronics of CH Activation by Energy Decomposition Analysis: From Transition Metals to Main-Group Metals
Abstract
Alkane CH activation is a fundamental reaction class where a metal-ligand complex reacts with a CH bond to give a metal-alkyl organometallic intermediate. CH activation reactions have been reported for a variety of transition metals and main-group metals. This chapter highlights recent quantum-mechanical studies that have used energy decomposition analysis (EDA) to provide insight into σ-coordination complexes and transition states for alkane CH activation reactions. These studies have provided new conceptual understanding of CH activation reactions and detailed insight into the physical nature and magnitude of interaction between alkanes with transition metals and main-group metals.
Clinton R. King, Samantha J. Gustafson, Daniel H. Ess
Backmatter
Metadata
Title
Computational Studies in Organometallic Chemistry
Editors
Stuart A. Macgregor
Odile Eisenstein
Copyright Year
2016
Electronic ISBN
978-3-319-31638-3
Print ISBN
978-3-319-31636-9
DOI
https://doi.org/10.1007/978-3-319-31638-3

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