Activation and Functionalization of C-H Bonds

by Goldberg, Karen I.; Goldman, Alan S.

• ISBN13: 9780841238497
• ISBN10: 0841238499
• Format: Hardcover
• Copyright: 2004-08-12
• Publisher: American Chemical Society

Summary

Activation and Functionalization of C-H Bonds explores recent developments in the reaction chemistry of solution-phase transition-metal based systems with simple hydrocarbons and with more complex organic molecules. More than 20 internationally leading research groups contributed to this volume, and their chapters cover such topics as fundamental theoretical and mechanistic studies of C-H bond activation by metal complexes, catalytic systems for alkane functionalization, and new applications in synthetic organic chemistry. An introductory chapter offers an overview of stoichiometric and catalytic reactions of C-H bonds with transition metal complexes. The C-H bond is the most widespread linkage in organic chemistry, present in virtually every organic molecule. Unfortunately, C-H bonds are famously resistant to selective chemical transformations. The development of methods for their selective transformations has enormous potential value in fields ranging from the chemistry of fuels (for example, the conversion of methane to methanol) to the synthesis of the most complex organic molecules.

Table of Contents

Preface	xiii
1. Organometallic C-H Bond Activation: An Introduction	1	(45)
Alan S. Goldman and Karen I. Goldberg
Oxidative Addition Reactions
2. C-H Bond Activation by Iridium and Rhodium Complexes: Catalytic Hydrogen-Deuterium Exchange and C-C Bond-Forming Reactions	46	(10)
Steven R. Klei, Kian L. Tan, Jeffrey T. Golden, Cathleen M. Yung, Reema K. Thalji, Kateri A. Ahrendt, Jonathan A. Ellman, T. Don Tilley, and Robert G. Bergman
3. Alkane Complexes as Intermediates in C-H Bond Activation Reactions	56	(14)
William D. Jones, Andrew J. Vetter, Douglas D. Wick, and Todd O. Northcutt
4. C-C versus C-H Bond Oxidative Addition in PCX (X=P,N,O) Ligand Systems: Facility, Mechanism, and Control	70	(16)
Boris Rybtchinski and David Milstein
5. Kinetic and Equilibrium Deuterium Isotope Effects for C-H Bond Reductive Elimination and Oxidative Addition Reactions Involving the Ansa-Tungstenocene Methyl-Hydride Complex [Me2Si(C5Me4)2]W(Me)H	86	(19)
Kevin E. Janak, David G. Churchill, and Gerard Parkin
6. Alkane C-H Bond Activation by O-Donor Ir Complexes	105	(11)
Gaurav Bhalla, Xiang Yang Liu, Antek Wong-Foy, C.J. Jones, and Roy A. Periana
7. Lanthanide Complexes: Electronic Structure and H-H, C-H, and Si-H Bond Activation from a DFT Perspective	116	(20)
Lionel Perrin, Laurent Maron, and Odile Eisenstein
C-H Bond Activations in Organic Synthesis, Alkane Dehydrogenation, and Related Chemistry
8. Catalytic, Thermal, Regioselective Functionalization of Alkanes and Arenes with Borane Reagents	136	(19)
John F. Hartwig
9. C-H Bond Functionalization in Complex Organic Synthesis	155	(14)
Dalibor Sames
10. Pincer and Chelate N-Heterocyclic Carbene Complexes of Rh, Ir, and Pd: Synthetic Routes, Dynamics, Catalysis, Abnormal Binding, and Counterion Effects	169	(15)
Anthony R. Chianese and Robert H. Crabtree
11. Sequential Hydrocarbon C-H Bond Activations by 16-Electron Organometallic Complexes of Molybdenum and Tungsten	184	(14)
Peter Legzdins and Craig B. Pamplin
12. Alkane Transfer-Dehydrogenation Catalyzed by a Pincer-Ligated Iridium Complex	198	(18)
Alan S. Goldman, Kenton B. Renkema, Margaret Czerw, and Karsten Krogh-Jespersen
13. DFT Calculations on the Mechanism of (PCP)Ir-Catalyzed Acceptorless Dehydrogenation of Alkanes: Realistic Computational Models and Free Energy Considerations	216	(34)
Karsten Krogh-Jespersen, Margaret Czerw, and Alan S. Goldman
14. Double Cyclometalation: Implications for C-H Oxidative Addition with PCP Pincer Compounds of Iridium 234 Hani A.Y. Mohammad, Jost C. Grimm, Klaus Eichele,
Hans-Georg Mack, Bernd Speiser, Filip Novak, William C. Kaska, and Hermann A. Mayer
Activation of C-H Bonds by Pt(II) (Shilov) Chemistry
15. C-H Bond Activation at Pt(II): A Route to Selective Alkane Oxidation?	250	(14)
Alan F. Heyduk, H. Annita Zhong, Jay A. Labinger, and John E. Bercaw
16. Competitive Trapping of Equilibrating Pt(IV) Hydridoalkyl and Pt(II) Alkane Complexes: A Valuable Tool for the Mechanistic Investigation of C-H Activation Reactions	264	(19)
Mats Tilset, Lars Johansson, Martin Lersch, and Bror J. Wik
17. Mechanisms of Reactions Related to Selective Alkane Oxidation by Pt Complexes	283	(20)
Jennifer L. Look, Ulrich Fekl, and Karen I. Goldberg
18. Hydrocarbon C-H Bond Activation with Tp'Pt Complexes	303	(16)
Cynthia M. Norris and Joseph L. Templeton
19. C-H Bond Activation with Neutral Platinum Methyl Complexes	319	(15)
Carl N. Iverson, Charles A. G. Carter, John D. Scollard, Melanie A. Pribisko, Kevin D. John, Brian L. Scott, R. Tom Baker, John E. Bercaw, and Jay A. Labinger
20. Issues Relevant to C-H Activation at Platinum(II): Comparative Studies between Cationic, Zwitterionic, and Neutral Platinum(II) Compounds in Benzene Solution	334	(22)
Jonas C. Peters, J. Christopher Thomas, Christine M. Thomas, and Theodore A. Betley
Oxidations
21. Non-Organometallic Mechanisms for C-H Bond Oxidation: Hydrogen Atom versus Electron versus Hydride Transfer	356	(14)
James M. Mayer, Anna S. Larsen, Jasmine R. Bryant, Kun Wang, Mark Lockwood, Gordon Rice, and Tae-Jin Won
22. Oxidation of Organic Molecules with Molecular Oxygen Catalyzed by Heterometallic Complexes	370	(9)
Patricia A. Shapley
23. Catalytic Hydrocarbon Oxidations Involving Coreductants	379	(14)
Joseph E. Remias and Ayusman Sen
24. New Applications of Electrophilic Aromatic C-H Activation with Metal Trifluoroacetates	393	(14)
Vladimir V. Grushin, David L. Thorn, William J. Marshall, and Viacheslav A. Petrov
25. Reengineering of Organic-Based Metal Active Sites for Oxidations and Oxygenations	407
Sergiu M. Gorun
Indexes
Author Index	424	(2)
Subject Index	426