Computational Modeling for Homogeneous and Enzymatic Catalysis: A Knowledge–Base for Designing Efficient Catalysis

Here, the world′s most active and productive computational scientists from academia and industry present established, effective and powerful tools for understanding catalysts. With its broad scope –– nitrogen fixation, polymerization, C–H bond activation, oxidations, biocatalysis and much more –– this book represents an extensive knowledge base for designing efficient catalysts, allowing readers to improve the performance of their own catalysts.

Spis treści:
Preface.
List of Contributors.
1 Computational Insights into the Structural Properties and Catalytic Functions of Selenoprotein Glutathione Peroxidase (GPx) (Rajeev Prabhakar, Keiji Morokuma, and Djamaladdin G. Musaev).
1.1 Introduction.
1.2 Catalytic Functions.
1.3 Computational Details.
1.4 Results and Discussion.
1.5 Summary.
References.
2 A Comparison of Tetrapyrrole Cofactors in Nature and their Tuning by Axial Ligands (Kasper P. Jensen, Patrik Rydberg, Jimmy Heimdal, and Ulf Ryde).
2.1 Introduction.
2.2 Methodology.
2.3 Comparison of the Intrinsic Chemical Properties of the Tetrapyrroles.
2.4 Tuning of Tetrapyrrole Structure and Function by Axial Ligands.
2.5 Concluding Remarks.
References.
3 Modeling of Mechanisms for Metalloenzymes where Protons and Electrons Enter or Leave (Per E. M. Siegbahn and Margareta R. A. Blomberg).
3.1 Introduction.
3.2 Energy Diagrams.
3.3 Conclusions.
References.
4 Principles of Dinitrogen Hydrogenation: Computational Insights (Djamaladdin G. Musaev, Petia Bobadova–Parvanova, and Keiji Morokuma).
4.1 Introduction.
4.2 Reaction Mechanism of the Coordinated Dinitrogen Molecule in Di–zirconocene–N2 Complexes with a Hydrogen Molecule.
4.3 Factors Controlling the N2 Coordination Modes in the Di–zirconocene–N2 Complexes.
4.4 Why the Complex Cannot Add a H2< /sub> Molecule to the Side–on Coordinated N2, while its Zr– and Hf–analogs Can.
4.5 Why Dizirconium–dinitrogen Complexes with bis(Amidophosphine) (P2N2) and Cyclopentadienyl (Cp) Ligands React differently with the Hydrogen Molecule: Role of Ligand Environment of the Zr Centers.
4.6 Several Necessary Conditions for Successful Hydrogenation of a Coordinated Dinitrogen Molecule.
Appendix: Computational Details.
References.
5 Mechanism of Palladium–catalyzed Cross–coupling Reactions (Ataualpa A. C. Braga, Gregori Ujaque, and Feliu Maseras).
5.1 Introduction.
5.2 Oxidative Addition.
5.3 Transmetalation.
5.4 Reductive Elimination.
5.5 Isomerization.
5.6 Concluding Remarks.
References.
6 Transition Metal Catalyzed CarbonxCarbon Bond Formation: The Key of Homogeneous Catalysis (Valentine P. Ananikov, Djamaladdin G. Musaev, and Keiji Morokuma).
6.1 Introduction.
6.2 CaC Coupling of Unsaturated Ligands.
6.3 Conclusions.
References.
7 Olefin Polymerization Using Homogeneous Group IV Metallocenes (Robert D. J. Froese).
7.1 Introduction.
7.2 Computational Details.
7.3 Results and Discussion.
7.4 Conclusions.
References.
8 Group Transfer Polymerization of Acrylates with Mono Nuclear Early d– and f–block Metallocenes. A DFT Study (Simone Tomasi and Tom Ziegler).
8.1 Introduction.
8.2 Computational Details.
8.3 Discussion.
8.4 Conclusions.
References.
9 Insights into the Mechanism of H2O2–based Olefin Epoxidation Catalyzed by the Lacunary [&amp;Alpha;–(SiO4) W10O32H4]4– and di–V–substituted–&amp;Alpha;–Keggin [&amp;Alpha;–1,2–H2SiV2W10O40]4– Polyoxometalates. A C omputational Study (Rajeev Prabhakar, Keiji Morokuma, Yurii V. Geletii, Craig L. Hill, and Djamaladdin G. Musaev)
9.1 Introduction.
9.2 Computational Details.
9.3 Results and Discussion.
9.4 Polyoxometalate–catalyzed Ethylene Epoxidation by Hydrogen Peroxide. Comparison of the Hydroxyl Mechanism involving Complexes 1 and 2.
References.
10 C–H Bond Activation by Transition Metal Oxides (Joachim Sauer).
10.1 Introduction.
10.2 Gas Phase and Surface Species Considered.
10.3 Oxidation of Methanol to Formaldehyde.
10.4 Oxidative Dehydrogenation of Alkanes on Supported Transition Metal Oxide Catalysts.
10.5 CaH Activation of Alkanes by Transition Metal Oxide Species in the Gas Phase.
10.6 Conclusions.
References.
11 Mechanism of Ru– and Mo–catalyzed Olefin Metathesis (Andrea Correa, Chiara Costabile, Simona Giudice, and Luigi Cavallo).
11.1 Introduction.
11.2 Models and Computational Details.
11.3 Results and Discussion.
11.4 Conclusions.
References.
12 Heterolytic s–Bond Activation by Transition Metal Complexes (Shigeyoshi Sakaki, Noriaki Ochi, and Yu–ya Ohnishi).
12.1 Introduction.
12.2 Characteristic Features of Heterolytic s–Bond Activation.
12.3 Heterolytic CaH s–Bond Activation of Methane.
12.4 Heterolytic s–Bond Activation of Dihydrogen and Alcohol Molecules.
12.5 Summary.
References.
13 Hydrosilylation Reactions Discovered in the Last Decade: Combined Experimental and Computational Studies on the New Mechanisms (Yun–Dong Wu, Lung Wa Chung, and Xin–Hao Zhang).
13.1 Introduction.
13.2 General Mechanistic Pathways in the 20th Century.
13.3 New Mechanistic Pathways Discovered at the Beginning of the 21st Century.
13.4 Conclusion.
References.
14 Methane Hydroxylation by First Row Transition Metal Oxides (Kazun ari Yoshizawa).
14.1 Introduction.
14.2 Reactivity of the MOþ Species.
14.3 Energy Profile for Methane Hydroxylation.
14.4 Intrinsic Reaction Coordinate (IRC) Analysis.
14.5 Spin–Orbit Coupling (SOC) in Methane Hydroxylation.
14.6 Kinetic Isotope Effect (KIE) for H–atom Abstraction.
14.7 Regioselectivity in Alkane Hydroxylation.
14.8 Concluding Remarks.
References.
15 Two State Reactivity Paradigm in Catalysis. The Example of X–H (X=O, N, C) and C–C Bonds Activation Mediated by Transition Metal Compounds (Maria del Carmen Michelini, Ivan Rivalta, Nino Russo, and Emilia Sicilia).
15.1 Introduction.
15.2 General Methods.
15.3 Activation of X–H (X=O, N, C) Bonds by First–row Transition Metal Cations.
15.4 Activation of C–C Bond: Cyclotrimerization of Acetylene by Second–row Transition Metal Atoms.
15.5 Use of the Electron Localization Function to Characterize the Bonding Evolution in Reactions involving Transition Metals.
References.
Subject Index.

Nota biograficzna:
Keiji Morokuma is William H. Emerson Professor Emeritus of Chemistry at Emory University in Atlanta, USA, and also Research Leader at Fukui Institute for Fundamental Chemistry at Kyoto University, Japan. Prof. Morokuma has authored over 600 scientific publications and has received numerous scientific awards, including Chemical Society of Japan Award, Schrodinger Medal from World Association of Theoretical Organic Chemists, Fukui Medal of Asian–Pacific Association of Theoretical and Computational Chemists. He was President of International Academy of Quantum Molecular Science from 2000–2006.
Jamal Musaev is the principal scientist and manager of the Emerson Center at Emory University in Atlanta, USA. Dr. Musaev has authored over 200 scientific publications and delivered numerous invited scientific lectures at universities and R