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E-raamat: Understanding Organometallic Reaction Mechanisms and Catalysis: Computational and Experimental Tools

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  • Ilmumisaeg: 25-Aug-2014
  • Kirjastus: Blackwell Verlag GmbH
  • Keel: eng
  • ISBN-13: 9783527678242
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Understanding Organometallic Reaction Mechanisms and Catalysis: Computational and Experimental ToolsSuurem pilt
  • Formaat: PDF+DRM
  • Ilmumisaeg: 25-Aug-2014
  • Kirjastus: Blackwell Verlag GmbH
  • Keel: eng
  • ISBN-13: 9783527678242
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Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book.

The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions.

An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.
List of Contributors XI
Preface XV
1 Mechanisms of Metal-Mediated C-N Coupling Processes: A Synergistic Relationship between Gas-Phase Experiments and Computational Chemistry 1(16)
Robert Kretschmer
Maria Schlangen
Helmut Schwarz
1.1 Introduction
1(1)
1.2 From Metal-Carbon to Carbon-Nitrogen Bonds
2(6)
1.2.1 Thermal Reactions of Metal Carbide and Metal Methylidene Complexes with Ammonia
2(2)
1.2.2 How Metals Control the C-N Bond-Making Step in the Coupling of CH4 and NH3
4(2)
1.2.3 C-N Coupling via SN2 Reactions: Neutral Metal Atoms as a Novel Leaving Group
6(2)
1.3 From Metal-Nitrogen to Carbon-Nitrogen Bonds
8(4)
1.3.1 High-Valent Iron Nitride and Iron Imide Complexes
8(3)
1.3.2 Metal-Mediated Hydroamination of an Unactivated Olefin by [ Ni(NH2)]+
11(1)
1.4 Conclusion and Perspectives
12(2)
Acknowledgments
14(1)
References
14(3)
2 Fundamental Aspects of the Metal-Catalyzed C-H Bond Functionalization by Diazocarbenes: Guiding Principles for Design of Catalyst with Non-redox-Active Metal (Such as Ca) and Non-Innocent Ligand 17(24)
Adrian Varela-Alvarez
Djamaladdin G. Musaev
2.1 Introduction
17(8)
2.1.1 Electronic Structure of Free Carbenes
20(2)
2.1.2 Electronic Structure of Metallocarbenes
22(3)
2.2 Theoretical Models and Methods
25(1)
2.3 Design of Catalyst with Non-redox-Active Metal and Non-Innocent Ligand
26(9)
2.3.1 The Proposed Catalyst: a Coordinatively Saturated Ca(II) Complex
26(1)
2.3.2 Potential Energy Surface of the [ (PDI)Ca(THF)3] Catalyzed C-H Bond Alkylation of MeCH2Ph by Unsubstituted N2CH2 Diazocarbene
27(5)
2.3.3 [ (PDI)Ca(THF)3]-Catalyzed C-H Bond Alkylation of MeCH2Ph by Donor-Donor (D/D) Diazocarbene N2CPh2
32(3)
2.4 Conclusions and Perspectives
35(2)
Acknowledgment
37(1)
References
37(4)
3 Using Metal Vinylidene Complexes to Probe the Partnership Between Theory and Experiment 41(28)
John M. Slattery
Jason M. Lynam
Natalie Fey
3.1 Introduction
41(3)
3.1.1 The Partnership between Theory and Experiment
41(1)
3.1.2 Transition-Metal-Stabilized Vinylidenes
42(2)
3.2 Project Planning in Organometallic Chemistry
44(5)
3.2.1 Experimental Methodologies
44(2)
3.2.2 Computational Methodologies
46(3)
3.3 Case Studies
49(14)
3.3.1 Mechanism of Rhodium-Mediated Alkyne to Vinylidene Transformation
50(4)
3.3.2 Using Ligand Assistance to Form Ruthenium-Vinylidene Complexes
54(4)
3.3.3 Vinylidenes in Gold Catalysis
58(3)
3.3.4 Metal Effects on the Alkyne/Vinylidene Tautomer Preference
61(2)
3.4 The Benefits of Synergy and Partnerships
63(1)
References
64(5)
4 Ligand, Additive, and Solvent Effects in Palladium Catalysis - Mechanistic Studies En Route to Catalyst Design 69(24)
Franziska Schoenebeck
4.1 Introduction
69(2)
4.2 The Effect of Solvent in Palladium-Catalyzed Cross Coupling and on the Nature of the Catalytically Active Species
71(4)
4.3 Common Additives in Palladium-Catalyzed Cross-Coupling Reactions - Effect on (Pre)catalyst and Active Catalytic Species
75(4)
4.4 Pd(I) Dimer: Only Precatalyst or Also Catalyst?
79(2)
4.5 Investigation of Key Catalytic Intermediates in High-Oxidation-State Palladium Chemistry
81(6)
4.6 Concluding Remarks
87(1)
References
88(5)
5 Computational Studies on Sigmatropic Rearrangements via π-Activation by Palladium and Gold Catalysts 93(28)
Osvaldo Gutierrez
Marisa C. Kozlowski
5.1 Introduction
93(1)
5.1.1 Sigmatropic Rearrangements
93(1)
5.1.2 Metal-Catalyzed Sigmatropic Rearrangements
93(1)
5.2 Palladium as a Catalyst
94(9)
5.2.1 Palladium Alkene Activation
94(9)
5.2.1.1 [ 3,3]-Sigmatropic Rearrangements
94(7)
5.2.1.2 [ 2,3]-Sigmatropic Rearrangements
101(2)
5.2.2 Palladium Alkyne Activation
103(1)
5.3 Gold as a Catalyst
103(14)
5.3.1 Gold Alkene Activation
103(5)
5.3.1.1 [ 3,3]-Sigmatropic Rearrangements
103(5)
5.3.2 Gold Alkyne Activation
108(41)
5.3.2.1 [ 3,3]-Sigmatropic Rearrangements
108(9)
5.4 Concluding Remarks
117(1)
References
117(4)
6 Theoretical Insights into Transition Metal-Catalyzed Reactions of Carbon Dioxide 121(24)
Ting Fan
Zhenyang Lin
6.1 Introduction
121(1)
6.2 Theoretical Methods
122(1)
6.3 Hydrogenation of CO2 with H2
122(5)
6.4 Coupling Reactions of CO2 and Epoxides
127(4)
6.5 Reduction of CO2 with Organoborons
131(3)
6.6 Carboxylation of Olefins with CO2
134(1)
6.7 Hydrocarboxylation of Olefins with CO2 and H2
134(3)
6.8 Summary
137(2)
Acknowledgment
139(1)
References
139(6)
7 Catalytically Enhanced NMR of Heterogeneously Catalyzed Hydrogenations 145(42)
Vladimir V. Zhivonitko
Kirill V. Kovtunov
Ivan V. Skovpin
Danila A. Barskiy
Oleg G. Salnikov
Igor V. Koptyug
7.1 Introduction
145(1)
7.2 Parahydrogen and PHIP Basics
146(3)
7.3 PHIP as a Mechanistic Tool in Homogeneous Catalysis
149(6)
7.3.1 PHIP-Enhanced NMR of Reaction Products
150(2)
7.3.2 PHIP Studies of Reaction Intermediates
152(1)
7.3.3 Activation of H2 and Structure and Dynamics of Metal Dihydride Complexes
153(2)
7.4 PHIP-Enhanced NMR and Heterogeneous Catalysis
155(25)
7.4.1 PHIP with Immobilized Metal Complexes
155(9)
7.4.2 PHIP with Supported Metal Catalysts
164(9)
7.4.3 Model Calculations Related to Underlying Chemistry in PHIP
173(7)
7.5 Summary and Conclusions
180(1)
Acknowledgments
180(1)
References
181(6)
8 Combined Use of Both Experimental and Theoretical Methods in the Exploration of Reaction Mechanisms in Catalysis by Transition Metals 187(30)
Daniel Lupp
Niels Johan Christensen
Peter Fristrup
8.1 Introduction
187(3)
8.1.1 Hammett Methodology
187(1)
8.1.2 Kinetic Isotope Effects
188(1)
8.1.3 Competition Experiments
189(1)
8.2 Recent DFT Developments of Relevance to Transition Metal Catalysis
190(7)
8.2.1 Computational Efficiency
191(2)
8.2.2 Dispersion Effects
193(2)
8.2.3 Solvation
195(1)
8.2.4 Effective Core Potentials
196(1)
8.2.5 Connecting Theory with Experiment
197(1)
8.3 Case Studies
197(16)
8.3.1 Rhodium-Catalyzed Decarbonylation of Aldehydes
198(5)
8.3.2 Iridium-Catalyzed Alkylation of Alcohols with Amines
203(2)
8.3.3 Palladium-Catalyzed Allylic C-H Alkylation
205(4)
8.3.4 Ruthenium-Catalyzed Amidation of Alcohols
209(4)
8.4 Conclusions
213(1)
Acknowledgments
214(1)
References
214(3)
9 Is There Something New Under the Sun? Myths and Facts in the Analysis of Catalytic Cycles 217(32)
Sebastian Kozuch
9.1 Introduction
217(1)
9.1.1 Prologue
217(1)
9.1.2 A Brief History of Catalysis
217(1)
9.2 Kinetics Based on Rate Constants or Energies
218(9)
9.2.1 Kinetic Graphs
220(2)
9.2.2 TOF Calculation of Any Cycle
222(3)
9.2.3 TOF in the E-Representation
225(2)
9.3 Application: Cross-Coupling with a Bidentate Pd Complex
227(3)
9.4 A Century of Sabatier's Genius Idea
230(2)
9.5 Theory and Practice of Catalysis, Including Concentration Effects
232(7)
9.5.1 Application: Negishi Cross-Coupling with a Ni Complex
233(3)
9.5.2 Can a Reaction Be Catalyzed in Both Directions?
236(3)
9.5.3 The Power Law
239(1)
9.6 RDStep[ X], RDStates[ /]
239(5)
9.6.1 Finding the RDStates
242(1)
9.6.2 Finding the Irreversible Steps
243(1)
9.7 Conclusion
244(2)
9.7.1 The Last Myth: Defining the TOF
244(1)
9.7.2 Final Words about the E-Representation
245(1)
References
246(3)
10 Computational Tools for Structure, Spectroscopy and Thermochemistry 249(72)
Vincenzo Barone
Malgorzata Biczysko
Ivan Carnimeo
10.1 Introduction
249(2)
10.2 Basic Concepts
251(9)
10.2.1 Potential Energy Surface: Molecular Structure, Transition States, and Reaction Paths
251(3)
10.2.2 DFT and Hybrid Approaches for Organometallic Systems
254(3)
10.2.3 Description of Environment
257(3)
10.3 Spectroscopic Techniques
260(27)
10.3.1 Rotational Spectroscopy
261(6)
10.3.1.1 Identification of Conformers/Tautomers
263(3)
10.3.1.2 Accurate Equilibrium Structures
266(1)
10.3.2 Vibrational Spectroscopy
267(13)
10.3.2.1 Frequencies
267(3)
10.3.2.2 Infrared and Raman Intensities
270(3)
10.3.2.3 Effective Treatment of Fermi Resonances
273(2)
10.3.2.4 Thermochemistry
275(2)
10.3.2.5 Approximate Methods: Hybrid Force Fields
277(2)
10.3.2.6 Approximate Methods: Reduced Dimensionality VPT2
279(1)
10.3.3 Electronic Spectroscopy
280(7)
10.3.3.1 General Framework for Time-Independent and Time-Dependent Computations of Vibronic Spectra
280(3)
10.3.3.2 Approximate Description of Excited State PES
283(4)
10.4 Applications and Case Studies
287(21)
10.4.1 Thermodynamics and Vibrational Spectroscopy Beyond Harmonic Approximation: Glycine and Its Metal Complexes
287(10)
10.4.1.1 Accurate Results for Isolated Glycine from Hybrid CC/DFT Computations
287(3)
10.4.1.2 Glycine Adsorbed on the (100) Silicon Surface
290(1)
10.4.1.3 Glycine-Metal Binding
291(6)
10.4.2 Optical Properties of Organometallic Systems
297(5)
10.4.2.1 Metal Complexation effects on the Structure and UV—Vis Spectra of Alizarin
297(4)
10.4.2.2 Luminescent Organometallic Complexes of Technological Interest
301(1)
10.4.3 Interplay of Different Effects: The Case of Chlorophyll-a
302(6)
10.5 Conclusions and Future Developments
308(1)
Acknowledgments
309(1)
References
309(12)
11 Computational Modeling of Graphene Systems Containing Transition Metal Atoms and Clusters 321(54)
Mikhail V. Polynski
Valentine P. Ananikov
11.1 Introduction
321(1)
11.2 Quantum Chemical Modeling and Benchmarking
322(19)
11.2.1 Electron Correlation Methods
322(2)
11.2.1.1 Truncated Coupled Cluster Methods
322(1)
11.2.1.2 Truncated Quadratic Configuration Interaction Methods
323(1)
11.2.1.3 Methods of Moller-Plesset Perturbation Theory
323(1)
11.2.2 Dispersion-Accounting DFT Methods
324(10)
11.2.2.1 Empirically Corrected DFT Methods
325(5)
11.2.2.2 Density Functionals with Nonlocal Correlation Term
330(4)
11.2.3 Database and Benchmarking Considerations
334(6)
11.2.3.1 S22, S66, and Related Databases
334(3)
11.2.3.2 Databases of Relatively Large Intermolecular Systems
337(1)
11.2.3.3 DFT Methods Benchmarking against Systems with Transition Metal Species
338(2)
11.2.4 Outlook on Database and Benchmarking
340(1)
11.3 Representative Studies of Graphene Systems with Transition Metals
341(21)
11.3.1 Graphene Models
341(1)
11.3.2 Pristine Graphene as a Substrate for Transition Metal Particles
342(5)
11.3.2.1 Transition Metal Adatoms on Pristine Graphene
342(1)
11.3.2.2 Metal Clusters or Nanoparticles on Pristine Graphene
343(4)
11.3.3 Defective or Doped Graphene as a Support for Transition Metal Particles
347(5)
11.3.3.1 Transition Metal Adatoms on Doped or Defective Graphene
347(2)
11.3.3.2 Transition Metal Clusters on Doped or Defective Graphene
349(3)
11.3.4 Studies of Complex Graphene Systems with Transition Metals
352(3)
11.3.5 Modeling Chemical Transformations in Graphene/Transition Metal Systems
355(7)
11.4 Conclusions
362(1)
Acknowledgments
363(1)
List of Abbreviations
363(2)
References
365(10)
Index 375
Valentine Ananikov received his Ph.D. degree in 1999, Habilitation in 2003, and was appointed Professor and Laboratory Head of the ND Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences in 2005. In 2008 he was elected as a Member of Russian Academy of Sciences. In 2012 he became Professor of Chemistry, Department of Moscow State University. In 2013 he has received a Megagrant of Saint Petersburg State University and was appointed as Head of Laboratory of Cluster Catalysis. Valentine Ananikov was a recipient of the Russian State Prize for Outstanding Achievements in Science and Technology in 2004, a Science Support Foundation award in 2005, a Russian Academy of Sciences Medal in 2000. He was named a Liebig Lecturer by German Chemical Society in 2010, and was awarded the Balandin Prize for outstanding achievements in the field of catalysis in 2010. His scientific interests are focused on development of new concepts in transition metal and nanoparticle catalysis, sustainable organic synthesis and new methodology for mechanistic studies of complex chemical transformations. His research has been supported by grants of Russian Science Foundation, Russian Foundation of Basic Research and Grants of President of Russia. Valentine Ananikov is a member of the International Advisory Boards of Advanced Synthesis & Catalysis, Organometallics, Chemistry - An Asian Journal and OpenChemistry.
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