This book presents the synthetic methodologies as well as the properties and potential usage of various ruthenium-containing materials. Starting from the first examples of 'ruthenopolymers' reported in the 1970s to the 3D architectures now synthesized, these materials have shown their importance far beyond fundamental polymer science. As well as highlighting the remarkable properties and versatile applications, this book also addresses a key question related to the applications of such heavy-metal-containing materials from the perspective of achieving a sustainable future. This book is of interest to both materials scientists and chemists in academia and industry.

This book focuses on the computational modeling of organometallic reactivity. In recent years, computational methods, particularly those based on Density Functional Theory (DFT) have been fully incorporated into the toolbox of organometallic chemists' methods. Nowadays, energy profiles of multistep processes are routinely calculated, and detailed mechanistic pictures of the reactions arise from these calculations. This type of analysis is increasingly performed even by experimentalists themselves. The volume aims to connect established computational organometallics with the more recent theoretical and methodological developments applied to this field. This would allow broadening of the simulation scope toward emergent organometallic areas (as ligand design or photoactivated processes), to narrow the gap between calculations and experiments (microkinetic models) and even to discover new reactions (automated methods). Given the broad interest and extensive application that computational methods have reached within the organometallic community, this new volume will attract the interest of both experimental and computational organometallic chemists.

This book joins an international and interdisciplinary group of leading experts on the biomedical, energy and environmental applications of Metal-Organic Frameworks (MOFs). The resulting overview covers everything from the environmentally friendly and scale up synthesis of MOFs, their application in green energy generation and storage, and water purification to their use as drug delivery systems, biosensors, and their association with relevant macromolecules (genes, enzymes). This book is focused on the interest of MOFs in applications such as the leading -edge environmental (energy-related) and biomedical fields. The potential of MOFs in these areas is currently progressing at a fast pace, since the wide possibilities that MOFs offer in terms of composition, topology, incorporation of active species (in their porosity, on their external surface or within the framework), and post-synthetic modifications, among others. The aim here is to provide future research goals that emphasize relevant nuances to this class of materials as a whole.

This book systematically describes the design and synthesis of MOF-related materials and the electrochemical energy storage-related research in the field of batteries. It starts with an introduction to the synthesis of MOF-based materials and various MOF derivatives, such as MOF-derived porous carbon and MOF-derived metal nanoparticles. This is followed by highlighting the interesting examples for electrochemical applications, illustrating recent advances in battery, supercapacitor, and water splitting. This book is interesting and useful to a wide readership in the various fields of chemical science, materials science, and engineering.

This book presents Pd- and Ni-catalyzed transformations generating functionalized heterocycles. Transition metal catalysis is at the forefront of synthetic organic chemistry since it offers new and powerful methods to forge carbon-carbon bonds in high atom- and step-economy. In Chapter 1, the author describes a Pd- and Ni-catalyzed cycloisomerization of aryl iodides to alkyl iodides, known as carboiodination. In the context of the Pd-catalyzed variant, the chapter explores the production of enantioenriched carboxamides through diastereoselective Pd-catalyzed carboiodination. It then discusses Ni-catalyzed reactions to generate oxindoles and an enantioselective variant employing a dual ligand system. Chapter 2 introduces readers to a Pd-catalyzed diastereoselective anion-capture cascade. It also examines diastereoselective Pd-catalyzed aryl cyanation to synthesize alkyl nitriles, a method that generates high yields of borylated chromans as a single diastereomer, and highlights its synthetic utility. Lastly, Chapter 3 presents a Pd-catalyzed domino process harnessing carbopalladation, C-H activation and -system insertion (benzynes and alkynes) to generate spirocycles. It also describes the mechanistic studies performed on these reactions.

This book describes novel synthetic methodologies for two kinds of structurally elaborate metal complexes: a heterometallic complex and a tetrahedral chiral-at-metal complex. The book provides the tools and inspiration to chemists for development of metal complexes with wide structural diversity than had previously been possible. For each of the two topics, existing synthetic methods for similar compounds are discussed first, and then new strategies are presented, followed by the demonstration of the synthesis of novel compounds supported by experimental results. Both of the final products in this research, a Co-Ni heterometallic complex covered in the first topic and a tetrahedral chiral-at-metal complex in the second one are difficult to obtain by using common synthetic methods for thermodynamic reasons. This research achieved highly selective syntheses of these compounds using newly designed strategies that enable precise kinetic control. Such an approach will be useful for synthesizing other new metal complexes. Since the last century, organic chemistry has flourished with the development of a variety of synthetic techniques that make precise kinetic control possible. Coordination chemistry of 3d or main-group transition metals has been mainly based on simple one-step reactions that yield only thermodynamic products. The publication of this book helps pave the way to kinetically controlled precise syntheses of various metal complexes.

This edited volume focuses on the host-guest chemistry of organic molecules and inorganic systems during synthesis (structure-direction). Organic molecules have been used for many years in the synthesis of zeolitic nanoporous frameworks. The addition of these organic molecules to the zeolite synthesis mixtures provokes a particular ordering of the inorganic units around them that directs the crystallization pathway towards a particular framework type; hence they are called structure-directing agents. Their use has allowed the discovery of an extremely large number of new zeolite frameworks and compositions. This volume covers the main aspects of the use of organic molecules as structure-directing agents for the synthesis of zeolites, including first an introduction of the main concepts, then two chapters covering state-of-the-art techniques currently used to understand the structure-directing phenomenon (location of molecules by XRD and molecular modeling techniques). The most recent trends in the types of organic molecules used as structure-directing agents are also presented, including the use of metal-complexes, the use of non-ammonium-based molecules (mainly phosphorus-based compounds) and the role of supramolecular chemistry in designing new large organic structure-directing agents produced by self-aggregation. In addition the volume explores the latest research attempting to transfer the asymmetric nature of organic chiral molecules used as structure-directing agents to the zeolite lattice to produce chiral enantioselective frameworks, one of the biggest challenges today in materials chemistry. This volume has interdisciplinary appeal and will engage scholars from the zeolite community with a general interest in microporous materials, which involves not only zeolite scientists, but also researchers working on metal-organic framework materials. The concepts covered will also be of interest for researchers working on the application of materials after encapsulation of molecules of interest in post-synthetic treatments. Further the work explores the main aspects of host-guest chemistry in hybrid organo-inorganic templated materials, which covers all types of materials where organic molecules are used as templates and are confined within framework-structured inorganic materials (intercalation compounds). Therefore the volume is also relevant to the wider materials chemistry community.

This book highlights and investigates novel solid-state luminescent properties of crystals with stimuli-responsive behavior. Several novel molecular designs for controlling crystal structures with photo-physical properties are described, with a special focus on external stimuli-responsive properties. The major goal of the material design concept was to capitalize on the chirality of crystals with stimuli-responsive properties. To allow crystals' chirality to be controlled and modified by means of external stimulation, the axial chirality of biaryl moiety was employed and, interestingly, produced several novel mechano- and vapo-responsive luminescent properties based on crystal-to-crystal or single-crystal-to-single-crystal phase transitions. In addition, the book details how the molecular rotation of luminophores in the solid phase can be used to achieve corresponding thermal-responsive phosphorescence. The reports presented here illustrate how the author has succeeded in controlling structural factors in a bulk environment by using molecular design with linking to photo-physical properties. The content will be of great interest to researchers in the field, and to members of chemical and material science societies.

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.

This thesis presents the latest developments in new catalytic C-C bond formation methods using easily accessible carboxylate salts through catalytic decarboxylation with good atom economy, and employing the sustainable element iron as the catalyst to directly activate C-H bonds with high step efficiency. In this regard, it explores a mechanistic understanding of the newly discovered decarboxylative couplings and the catalytic reactivity of the iron catalyst with the help of density functional theory calculation. The thesis is divided into two parts, the first of which focuses on the development of a series of previously unexplored, inexpensive carboxylate salts as useful building blocks for the formation of various C-C bonds to access valuable chemicals. In turn, the second part is devoted to several new C-C bond formation methodologies using the most ubiquitous transition metal, iron, as a catalyst, and using the ubiquitous C-H bond as the coupling partner.

The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience.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 are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.The chapter "Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates" is available open access under a CC BY 4.0 License via link.springer.com.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics in pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors.

Keeping up with the literature in a fast moving science discipline can be difficult so finding a distilled view of the latest progress in an area is invaluable. In this celebratory volume, the editors have approached leading researchers to review the area of organometallic chemistry spanning the years. This interdisciplinary field has the potential to provide answers to problems and challenges faced in catalysis, synthetic organic chemistry and unusal reactivity and the development of new materials. Providing a timely addition to the literature, this volume will reflect current interests as well as look at how these have developed over the years and even explore future applications.

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal

This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of -bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first -SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into -bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of -SiSi, -CC and -CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of -CC and -CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

This thesis reports the latest developments in the direct amination of various C H bonds using an H Zn exchange/electrophilic amination strategy. McDonald and co-workers reveal this approach to be a rapid and powerful method for accessing a variety of functionalized amines. The material outlined in this book shows how McDonald achieved C H zincation using strong, non-nucleophilic zinc bases and subsequent electrophilic amination of the corresponding zinc carbanions with copper as a catalyst and O-benzoylhydroxylamines as the electrophilic nitrogen source. McDonald's findings are of relevance to medicinal chemistry, drug discovery and materials science. Her thesis is a source of inspiration for scientists entering the field and students beginning their PhD in a related area.

A series of critical reviews and perspectives focussing on specific aspects of organometallic chemistry interfacing with other fields of study are provided. For this volume, the critical reviews cover topics such as the activation of "inert" carbon-hydrogen bonds, ligand design and organometallic radical species. For example, Charlie O'Hara discusses how mixed-metal compounds may perform the highly selective activation of C-H bonds and, in particular, how synergic relationships between various metals are crucial to this approach. The chemistry of a remarkable series of air-stable chiral primary phosphine ligands is discussed in some depth by Rachel Hiney, Arne Ficks, Helge M(3)ller-Bunz, Declan Gilheany and Lee Higham. This article focuses on the preparation of these ligands and also how they may be applied in various catalytic applications. Bas De Bruin reports on how ligand radical reactivity can be employed in synthetic organometallic chemistry and catalysis to achieve selectivity in radical-type transformations. As well as highlighting ligand-centered radical transformations in open-shell transition metals, an overview of the catalytic mechanism of Co(II)-catalysed olefin cyclopropanation is given, showing that enzyme-like cooperative metal-ligand-radical reactivity is no longer limited to real enzymes. Valuable and informative comprehensive reviews in the field of organometallic chemistry are also covered in this volume. For example, organolithium and organocuprate chemistry are reviewed by Joanna Haywood and Andrew Wheatley; aspects in Group 2 (Be-Ba) and Group 12 (Zn-Hg) compounds by Robert Less, Rebecca Melen and Dominic Wright; metal clusters by Mark Humphrey and Marie Cifuentes; and recent developments in the chemistry of the elements of Group 14 - focusing on low-coordination number compounds by Richard Layfield. This volume therefore covers many synthetic and applied aspects of modern organometallic chemistry which ought to be of interest to inorganic, organic and applied catalysis fields.

This volume presents the latest developments in the use of organometallic catalysis for the formation of bulk chemicals and the production of energy, via green processes including efficient utilization of waste feedstocks from industry. The chemistry of carbon dioxide relating to its hydrogenation into methanol -an eco-friendly energy storage strategy- and its uses as C1 synthon for the formation of important building-blocks for fine chemicals industry are covered. Catalytic hydrogenations of various functional groups and hydrogen transfer reactions including the use of first row metal catalysts are presented as well as the conversion of alcohols to carboxylates via hydrogen transfer with a zero-waste strategy using water. Transformation of renewable or bio-based raw materials is surveyed through alkene metathesis and C-O bond activations and functionalizations. A green aspect for selective formation of C-C, C-O and C-N bonds involves direct regioselective C-H bond activations and functionalizations. These transformations can now be promoted under mild reaction conditions due to the use photoredox catalyts. C-H bond oxidation using visible light leads mainly to the formation of C-O and C-N bonds, whereas cross-coupled C-C bonds can be formed through the radical additions on (hetero) arenes using photoredox assisted mechanism.

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. Review articles for the individual volumes are invited by the volume editors.
Readership: research scientists at universities or in industry, graduate students
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The work presented in Thomas M. Gogsig'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. Gogsig 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."

The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal