The authors of this volume concentrate on the recent progress of novel polyoxometalate (POM) syntheses, as well as advances made in catalytic, electrochemical, and sensing systems. The state-of-the-art techniques such as flow system and gel-electrophoresis for the discovery of POMs are covered with a detailed discussion. Of particular importance, the application of POM-based materials in photo-sensing, heterogeneous catalysis, energy conservation and storage, and gas separation is reviewed. Over the past few years, POM chemistry has witnessed a remarkable progress with more than 1500 papers published each year. Due to their intrinsic structural features, POMs are considered as versatile building blocks for the construction of sophisticated complex assemblies and advanced multi-functional materials. Various strategies, methods, and techniques have been adopted to develop POM-based materials with intriguing properties and excellent performance. All the contributors to this volume are young, vibrant chemists in this research field and all the works are carefully collected from the authors' years of experience. This volume serves as an essential reference for every POM chemist and is of great interest to new researchers who wish to learn more about this area.

The book focuses on the thermal transformations of various types of metal chelates, e.g. low molecular weight and polymeric metal chelates, coordination polymers and metal-organic frameworks. It analyzes the major advances and the problems in the preparation of metal oxide materials, mixed-oxide nanocomposites, carbon materials and polymer derived non-oxide nanocomposites by the thermolysis of different metal chelates. It also highlights the influence of the spatial and electronic structure of metal chelates on the mechanism and kinetics of their thermal transformations, and discusses important issues like conjugate thermolysis and computer modelling of the thermolysis process. This book is useful for researchers experienced in thermolysis as well as for young scientists interested in this area of science.

This thesis provides essential information on the systematic design of assembled lanthanide complexes for functional luminescent materials. It discusses the relationships between assembled structures and photo, thermal, and mechanical properties on the basis of crystallography, spectroscopy, and thermodynamics. The described guidelines for assembled structures will be extremely valuable, both for industrial applications and for readers' fundamental understanding of solid-state photophysics and materials chemistry. Luminescent lanthanide complexes are promising candidates for lighting devices, lasers, and bio-probes owing to their line-like and long-lived emission arising from characteristic 4f-4f transitions. Low-vibrational and asymmetrical coordination structures around lanthanide ions have been introduced to achieve strong luminescence, using specific organic ligands. Recently, assembled lanthanide complexes including coordination polymers and metal organic frameworks have increasingly attracted attention as a new class of luminescent materials offering thermal stability and color tunability. However, improving the luminescence efficiencies of these compounds remains a challenge, and specific molecular designs to control assembled structures and yield additional physical properties have not been established. The author provides a group of bent-angled bridging ligands to boost photoluminescence efficiency, and successfully introduces for the first time glass formability and strong triboluminescence properties.

This book investigates the use of palladium modified by bulky ligands as catalysts for new chemical transformations that rapidly assemble several classes of complex heterocyles. It documents the development of new chemical reactions involving carbon-carbon (C-C) and carbon-halogen (C-X) bond formation in the context of alkene difunctionalization and dearomatization reactions. Due to the ubiquity of heterocycles in bioactive natural products and life-improving pharmaceutical treatments, a long-term goal for synthetic organic chemists has been to develop novel and creative heterocycle syntheses that illicit a high degree of product diversity and are characterized by mild reaction conditions and limited waste production. A considerable fraction of leading pharmaceutical drugs contain at least one heterocycle within their chemical structure, and their prevalence in these technologies is strong evidence that the fundamental curiosities of organic chemistry lead to real-world solutions for the health and wellness of the global population.

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 abbrev iated as Top Organomet Chem and cited as a journal.

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 presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.

This outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metal-metal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.

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.

This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.

This book focuses on direct nitrogenation strategies to incorporate one or more N-atoms into simple substrates especially hydrocarbons via C-H and/or C-C bond cleavage, which is a green and sustainable way to synthesize nitrogen-containing compounds. The book consists of seven chapters demonstrating interesting advances in the preparation of amines, amides, nitriles, carbamides, azides, and N-heterocyclic compounds and illustrating the mechanisms of these novel transformations. It offers an accessible introduction to nitrogenation reactions for chemists involved in N-compound synthesis and those interested in discovering new reagents and reactions. Ning Jiao is a Professor of Chemistry at Peking University, China.

This book discusses recent progress in endohedral fullerenes - their production and separation techniques, as well as their characterization and properties. Furthermore, the book delves into the all-important issue of stability by investigating electron transfer between the encapsulated metal species and the carbon cage. It also reviews spin-based phenomena caused by the shielding of endohedral spin by the fullerene, and analyzes formation of the spin states by charge transfer as studied by electron spin resonance. Tuning of charge states of endohedral species and of spin states of both the cage and the cluster are explained. Finally, the book considers the recent discovery of magnetism in some endohedral fullerenes, and the potential for quantum computing.

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 brief summarizes the most commonly used sulfur dioxide surrogates and also shows the diverse reactivities to highlight the advances made in the development of synthetic methods through the insertion of sulfur dioxide. Depending on the nature of the transformation, these reactions are classified into four types: (i) pericyclic reactions; (ii) nucleophilic addition with organometallic reagents; (iii) transition metal catalysis; and (iv) free radical reactions. Highlighting recent advances in the insertion of sulfur dioxide, providing detailed descriptions of the experimental procedures for these valuable reactions, and discussing the remaining challenges in this field, the brief offers an appealing and highly useful guide for a wide readership in organic chemistry and medicinal chemistry from both academia and industry.

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. 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 book presents an in-depth study into the utility of σ-bond metathesis in Group 2 mediated reactivity. A comprehensive introduction defines the state of the art in both Group 2 mediated catalysis and dehydrocoupling. Structural investigations giving rise to a range of mixed s-block metal hydrides including a remarkable dodecabimetallic decahydride are then described. Subsequent extensive mechanistic work focussing on both silicon-nitrogen and boron-nitrogen dehydrocoupling gives insights into both congeneric effects down Group 2 and ligand effects centring upon magnesium. These studies show the striking effects of these factors, as well as the electronic nature of the hydridic coupling partner.  Finally, the unprecedented introduction of single-electron transfer steps into Group 2 catalytic manifolds is described. The use of the stable radical TEMPO to induce single-electron transfer to substituents bound to Group 2 centres coupled with σ-bond metathesis allows a novel hydrogen release from silanes.

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.

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. 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. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students.

Antoine Simonneau's thesis highlights the development of new cycloisomerization reactions through the activation of alkynes with gold complexes. First Simonneau describes 1,6-enynes and their direct conversion into allenes through 1,5-hydride or ester migration processes. The author and his team used appropriate propargylic functional groups to achieve this conversion. This study shows that O-tethered 1,6-enynes carrying a strained cycloalkane at the propargylic position could undergo a cyclopropanation/ring expansion cascade reaction. The author employed this rearrangement as the starting point in the design of a new macro cycle synthesis. The next part of the thesis focuses on the cycloisomerization of diynes involving as the first step of the process the rearrangement of one alkyne partner into an allene thanks to a gold-catalyzed 1,3-shift of a propargylic ester. The thesis discloses a new cycloisomerization pattern featuring a 1,5-carbonyl transfer, giving rise to unprecedented cross-conjugated diketones. In the final part of the research, Simmoneau investigates the gold-catalyzed cycloisomerization mechanism of 1,6-enynes and questions the intermediacy of gold acetylides. By the means of NMR and mass spectrometry analysis, theoretical treatment and solution experiments, it was possible to rule out the involvement of these species in the catalytic cycle. This thesis has led to a number of publications in high-impact journals.

In this thesis, the focus is on the study of new catalytic properties of unsupported nanoporous metals in heterogeneous organic reactions under liquid-phase conditions. The author was the first to fabricate nanoporous copper with tunable nanoporosity and apply it for organic reactions. The catalyst can be reused up to ten times without loss of catalytic activity. In addition, the author developed the highly selective semihydrogenation of alkynes using nanoporous gold as a catalyst for the first time, affording Z-alkenes in 100% selectivity, which cannot be realized by traditional catalysts. All of the results described here will help readers to develop new catalytic performance of nanoporous metals for organic reactions.

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.

Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic, and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles, and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science - as an introduction to a neighboring field, or as a compilation of detailed information for the specialist.

The application of molecules in technological devices hinges on the proper understanding of their behavior on metallic electrodes or substrates. The intrinsic molecular electronic and magnetic properties are modified at a metallic interface, and greatly depend on the atomic configuration of the molecule-metal bond. This poses certain problems, such as the lack of reproducibility in the transport properties of molecular junctions, but also offers the possibility to induce new charge and spin configurations that are only present at the interface. The results presented in this thesis address this issue, providing a comprehensive overview of the influence of molecule-metal and molecule-molecule interactions on the electronic and magnetic properties of molecules adsorbed on metallic substrates. Using metal-phthalocyanines (MePc), a commonly used metal-organic complex as a model system, each chapter explores different aspects of the interaction with silver surfaces: the local adsorption geometry, self-assembly, the modifications of the electronic and magnetic characteristics due to hybridization and charge transfer, and finally the manipulation of molecular charge and spin states by electron doping using alkali atoms moved with the STM tip.

This thesis describes the first and long-sought successful synthesis of a new pyrazole-expanded porphyrin, a higher analog of porphyrin. This "Siamese-Twin Porphyrin" provides two conjoined porphyrin-like coordination spheres, thus being able to accommodate two metal ions within the same ligand. In her thesis, Lina Blusch not only explains the challenging synthesis and characterization of the ligand system, but also its application to the synthesis of homo- and hetero-bimetallic Ni and Cu complexes. She observes interesting metal-metal-interactions in the complexes, that lead to a non-innocent multistep redox chemistry. The ligand system and its complexes show an intriguing twisted geometry, giving rise to helical chirality and other fascinating properties. This study explores the first steps and opens up a new chemistry of expanded porphyrins with the potential to biomimetic applications.