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The field of organometallic chemistry has emerged over the last twenty-five years or so to become one of the most important areas of chemistry, and there are no signs of abatement in the intense current interest in the subject, particularly in terms of its proven and potential application in catalytic reactions involving hydrocarbons. The development of the organometallic/ catalysis area has resulted in no small way from many contributions from researchers investigating palladium systems. Even to the well-initiated, there seems a bewildering and diverse variety of organic reactions that are promoted by palladium(II) salts and complexes. Such homogeneous reactions include oxidative and nonoxidative coupling of substrates such as olefins, dienes, acetylenes, and aromatics; and various isomerization, disproportionation, hydrogenation, dehydrogenation, car bonylation and decarbonylation reactions, as well as reactions involving formation of bonds between carbon and halogen, nitrogen, sulfur, and silicon. The books by Peter M. Maitlis - The Organic Chemistry of Palladium, Volumes I, II, Academic Press, 1971 - serve to classify and identify the wide variety of reactions, and access to the vast literature is available through these volumes and more recent reviews, including those of J. Tsuji [Accounts Chem. Res. , 6, 8 (1973); Adv. in Organometal. , 17, 141 (1979)], R. F. Heck [Adv. in Catat. , 26, 323 (1977)], and ones by Henry [Accounts Chem. Res. , 6, 16 (1973); Adv. in Organometal. , 13, 363 (1975)]. F. R. Hartley's book - The Chemistry of Platinum and Palladium, App!. Sci. Pub!.
This thesis focuses on investigating fundamental oxidative addition (OA) reactions catalysed by palladium. OA, being the first and rate determining step in cross-coupling reactions, is a reaction of vital importance in synthetic chemistry. The findings in this thesis were successfully obtained using the Activation Strain Model of chemical reactivity in combination with computations based on Density Functional Theory (DFT) as implemented in the ADF program. The ASM model is a fragment-based approach that characterizes reactions in terms of the rigidity and the bonding capabilities of the original reactants, and the extent to which the reactants must deform along the reaction pathway of a particular reaction mechanism. Thus, the total energy profile of a particular chemical reaction can be decomposed into contributions from the deformation of the reactants (the strain energy) and their mutual interaction (the interaction energy). The interaction energy can then be further decomposed using the canonical energy decomposition analysis of ADF into electrostatic interactions, destabilizing Pauli repulsion, and stabilizing orbital interactions. In Chapter 3, with the aim of understanding the underlying mechanism and trends found by the OA, we detailed our quantum chemical exploration of the palladium-mediated activation of C(spn)–X bonds (n = 1–3; X = F, Cl, Br, I) in the archetypal model substrates H3C–CH2–X, H2C=CH–X, and HC≡C–X by a model bare palladium catalyst. First and foremost, we investigated the bond dissociation enthalpies (BDEs) of the bonds to be activated. So, we started from the C(sp3)–X moving to C(sp2)–X and then to C(sp)–X bonds for each of the selected set of X atoms above. We found that as we move down group 17, the C(spn)–X bond becomes weaker and as such easier to break.
The work presented in Thomas M. Gøgsig's thesis deals with the discovery of new metal-catalyzed transformations ranging from Kumada-, Heck- and Suzuki-type reactions. The thesis starts with a formidable introduction to Pd-catalyzed cross-coupling reactions. New results have been obtained on: (i) Pd-catalyzed 1,2-migration reactions, (ii) Pd-catalyzed Heck reactions employing heteroaromatic tosylates, (iii) Ni-catalyzed Heck reactions, and (iv) Pd-catalyzed carbonylative Heck reaction. Metal-catalyzed cross-coupling reactions are today a highly competititve field (the 2010 Nobel Prize in Chemistry was awarded "for palladium-catalyzed cross couplings in organic synthesis", the 2001 and 2005 Nobel Prizes in closely related fields). Thomas M. Gøgsig obtained new results in his thesis that will help to improve the outcome of catalytic processes and improve their scope. The results will thus become key references for tomorrow's new applications. All chapters include insightful discussions and in-depth descriptions of the key principles of these new discoveries.
In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.
Exploring the importance of Richard F. Heck’s carbon coupling reaction, this book highlights the subject of the 2010 Nobel Prize in Chemistry for palladium-catalyzed cross couplings in organic synthesis, and includes a foreword from Nobel Prize winner Richard F. Heck. The Mizoroki-Heck reaction is a palladium-catalyzed carbon–carbon bond forming process which is widely used in organic and organometallic synthesis. It has seen increasing use in the past decade as chemists look for strategies enabling the controlled construction of complex carbon skeletons. The Mizoroki-Heck Reaction is the first dedicated volume on this important reaction, including topics on: mechanisms of the Mizoroki-Heck reaction intermolecular Mizoroki-Heck reactions focus on regioselectivity and product outcome in organic synthesis waste-minimized Mizoroki-Heck reactions intramolecular Mizoroki-Heck reactions formation of heterocycles chelation-controlled Mizoroki-Heck reactions the Mizoroki-Heck reaction in domino processes oxidative heck-type reactions (Fujiwara-Moritani reactions) Mizoroki-Heck reactions with metals other than palladium ligand design for intermolecular asymmetric Mizoroki-Heck reactions intramolecular enantioselective Mizoroki-Heck reactions desymmetrizing Mizoroki-Heck reactions applications in combinatorial and solid phase syntheses, and the development of modern solvent systems and reaction techniques the asymmetric intramolecular Mizoroki-Heck reaction in natural product total synthesis Several chapters are devoted to asymmetric Heck reactions with particular focus on the construction of otherwise difficult-to-obtain sterically congested tertiary and quaternary carbons. Industrial and academic applications are highlighted in the final section. The Mizoroki-Heck Reaction will find a place on the bookshelves of any organic or organometallic chemist. “I am convinced that this book will rapidly become the most important reference text for research chemists in academia and industry who seek orientation in the rapidly growing and – for the layman – confusing field described as the “’Mizoroki–Heck reaction’.” (Synthesis, March 2010)
Following on from its recognition in the 2010 Nobel Prize for Chemistry, contributors from across the globe present the latest cross-coupling trends in both academia and industry.
Kyle A. Grice, Margaret L. Scheuermann and Karen I. Goldberg: Five-Coordinate Platinum(IV) Complexes.- Jay A. Labinger and John E. Bercaw: The Role of Higher Oxidation State Species in Platinum-Mediated C-H Bond Activation and Functionalization.- Joy M. Racowski and Melanie S. Sanford: Carbon-Heteroatom Bond-Forming Reductive Elimination from Palladium(IV) Complexes.- Helena C. Malinakova: Palladium(IV) Complexes as Intermediates in Catalytic and Stoichiometric Cascade Sequences Providing Complex Carbocycles and Heterocycles.- Allan J. Canty and Manab Sharma: h1-Alkynyl Chemistry for the Higher Oxidation States of Palladium and Platinum.- David C. Powers and Tobias Ritter: Palladium(III) in Synthesis and Catalysis.- Marc-Etienne Moret: Organometallic Platinum(II) and Palladium(II) Complexes as Donor Ligands for Lewis-Acidic d10 and s2 Centers.