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Books > Science & Mathematics > Chemistry > Organic chemistry > Organometallic chemistry
This book provides an overview of the design, synthesis, and characterization of different photoactive hybrid organic-inorganic materials, based on the combination of mainly organic molecules and inorganic nanostructures, tackling their uses in different scientific fields from photonics to biomedicine. There are many examples extensively describing how the confinement of organic compounds (i.e. chromophores, photochromic molecules or photoreactants), or other photoactive compounds (i.e.metal clusters) into several microporous systems can modulate the photophysical properties and photochemical reactions leading to interesting applications. Among (ordered)-hosts, different systems of diverse nature are widely used, such as the, the 1D- or 3D- channels of zeolitic frameworks, interlayer space of 2D-clays, the organic nanospace of curcubituril and cyclodextrins or the organo-inorganic porous crystalline MOFs systems. This volume highlights the advances of these photoactive materials and aims to be an inspiration for researchers working in materials science and photochemistry, including chemists, material engineers, physicists, biologists, and medical researchers.
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 volume discusses the great potential of metal nanoparticle catalysts for complicated molecular synthesis and reviews the current progress of this field. The development of highly active and stable heterogeneous catalysts is a crucial subject in modern science. However, development of heterogeneous catalysts for fine chemical synthesis has lagged far behind those for bulk chemical process. In recent years metal nanoparticle catalysts have been of great interest in this area due to their unique activity, ease of heterogenization, and robustness. Therefore, metal nanoparticle catalysts are an excellent candidate for the above-mentioned active and robust heterogeneous catalysts and this book provides an overview of this area. The present volume summarizes recent progress on nanoparticle catalysis for various organic transformations from simple redox reactions to complex asymmetric C-C bond forming reactions and also presents seminal studies on new technologies. It comprehensively summarizes advances in metal nanoparticle catalysis across several aspects including reaction manners, mechanistic investigations and new synthetic methodologies to encourage the use of metal nanoparticle catalysts for future organic synthesis. This volume will be of interest to students, researchers and professionals focused on the next-generation of fine chemical synthesis.
Magnetic nanocatalysts are garnering attention for development of greener catalytic processes due to their ease of recovery from a reaction medium. This book delves into a variety of magnetic nanocatalysts, their use in the industrial context, and recyclability. Topics covered include wastewater treatment, drug delivery, and industrial catalysis; another available volume focuses on the use of magnetic nanocatalysts in synthetic appliances and transformations.
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.
Organoselenium shows incredible promise in medicine, particularly cancer therapy. This book discusses organoselenium chemistry and biology in the context of its therapeutic potential, taking the reader through synthetic techniques, bioactivity and therapeutic applications. Divided into three sections, the first section describes synthetic advances in bioactive selenium compounds, revealing how organoselenium compound toxicity, redox properties and specificity can be further tuned. The second section explains the biophysics and biochemistry of organoselenium compounds, as well as selenoproteins. The final section closes with several chapters devoted to therapeutic and medicinal applications of organoselenium compounds, covering radioprotectors, anticancer agents and antioxidant behaviour. With contributions from leading global experts, this book covers recent advances in the field and is an ideal reference for those researching organoselenium compounds.
This volume gives an overview of the applications of organometallic chemistry in process chemistry relevant to the current topics in synthetic chemistry. This volume starts with an introduction on the historical development of organometallics in process chemistry and is followed by chapters dealing with the last five years' development in various organometallic reaction types such as the challenging cross coupling process, construction of 3.1.0 bicycles, pressure and transfer hydrogenations of historically challenging compounds such as esters, utilization of carbon dioxide for making organic compounds by flow process, drug synthesis and metal detection and scavenging in the finished APIs. A chapter by Colacot et.al., is also devoted to the process development and structural understanding of organometallic catalysts with particular emphasis to LnPd(0) catalysts. An academia - industry collaborated chapter on the use of water as a solvent for organometallic processes is included in this book.
This book provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of significant recent developments in the area of metal-ligand cooperativity, with a focus on pincer architectures. The various contributions highlight the widespread impact of M-L co-operativity phenomena on modern organometallic chemistry and catalyst development. The development of efficient and selective catalytic transformations relies on the understanding and fine control of the various elementary reactions that constitutes a catalytic cycle. Co-operative ligands, which actively participate in bond making and bond breaking together to the metal they support, open up new avenues in this area. In particular, buttressing a weak or reactive metal-ligand bond by flanking coordinating arms in a pincer ligand design is proving a versatile strategy to access robust metal complexes that exhibit unusual and selective reactivity patterns.
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 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 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.
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.
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.
To appreciate the chemistry and physical properties of complexes of the transition series, an understanding of metal-ligand interactions applied to complexes of the d-block is needed. Metal Ligand Bonding aims to provide this through an accessible, detailed, non-mathematical approach. Initial chapters detail the crystal-field model, using it to describe the use of magnetic measurements to distinguish complexes with different electronic configurations and geometries. Subsequent chapters look at the molecular orbital theory of transition metal complexes using a pictorial approach. Bonding in octahedral complexes is explored and electronic spectra and magnetic properties are given extensive coverage. The material addressed in this book forms the foundation of undergraduate lecture courses on d-block chemistry and facilitates learning through various key features, including: full colour diagrams; in-text questions with answers; revision exercises and clearly defined learning outcomes to encourage a reflective approach to study; an associated website; and experimental data and observations from everyday life. A basic knowledge of atomic and molecular orbitals as applied to main group elements is assumed.
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 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 book cuts across the divisions of organic, inorganic, and physical chemistry. It describes new methods for creating -conjugated porphyrin oligomers with precisely defined sequences of zinc and copper metal cations, and how EPR spectroscopy was used to investigate the dipolar and exchange coupling between the paramagnetic copper(II) centres. Porphyrins are a group of heterocyclic macrocycle organic compounds that play an important role in our everyday life and can for example be found in blood where they form a red complex with iron (haem). Various metallic elements can be inserted into a porphyrin and changing the coordinated metal is an excellent way to influence the chemical and physical properties of these molecules. Focusing on 3 metals - zinc, magnesium and copper - the author established new methods for creating -conjugated porphyrin oligomers and lastly presents the synthesis and investigation of two novel porphyrin nanoballs. Giving the template-directed strategy the author developed for constructing these molecules, this work could provide access to other related nano-cages.
This volume highlights the recent advances and state of art in the experimental and theoretical studies of organometallic magnets. A plethora of organic ligands such as Mannich-base derivatives, redox-active chromophores, cyanides, Schiff base among others are used to coordinate to 3d transition metals, 4f lanthanides and 5f actinides to design the molecular magnets. Deep analysis of the coordination sphere symmetry, electronic distribution, luminescence are investigated to perform magneto-structural correlation leading to a better understanding of the magnetic properties. Furthermore, the rationalization of the magnetic behavior can be reached using ab initio calculations. The multiple applications that these molecular magnets offer could revolutionize the high-density data storage, spintronics and quantum computing technologies. This volume provides a discussion of these topics from leading international experts and will be a useful reference for researchers working in this field.
The demand for novel efficient and environmentally sustainable chemo, regio- and stereoselective catalyst systems for the oxidation of organic substrates is continuously growing in line with toughening economic and environmental constraints. This book addresses these issues; it consists of eleven chapters written by world-recognized experts in green and sustainable oxidation catalysis. The most urgent and challenging topics, in the judgment of the editor, such as green asymmetric epoxidations, sulfoxidatiuons, C-H oxidations; oxidation catalysis by polyoxometalates and oxidations in non-conventional solvents, etc. have been critically reviewed in this book. Both fundamental aspects, such as catalysts design, catalytic properties, nature of catalytically active sites and reaction mechanisms, and practical outlook of the oxidations have been addressed by the authors. The book appeals to a broad readership, particularly graduate students, employees of universities and research organizations, and industrial researchers, particularly those working in the areas of homogeneous oxidation catalysis, asymmetric synthesis, organocatalysis, sustainable catalytic processes and green chemistry, mechanisms of catalytic reactions, synthesis of bioactive compounds, biomimetic chemistry, etc. Konstantin Bryliakov is Leading Researcher at the Boreskov Institute of Catalysis. In 2016, he was elected Honorary Professor of the Russian Academy of Sciences.
As solid state chemistry becomes increasingly important,
organometallic chemistry will play a key role in addressing complex
structures and developing novel interface chemistry. In a
collection of reviews, leading chemists Focus on X-ray diffraction,
MAssbauer spectroscopy and solid-state NMR in an overview of
state-of-the-art structure analysis techniques and chemical
applications in the solid state. Solid State Organometallic
Chemistry
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.
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.
This volume discusses the great potential of metal nanoparticle catalysts for complicated molecular synthesis and reviews the current progress of this field. The development of highly active and stable heterogeneous catalysts is a crucial subject in modern science. However, development of heterogeneous catalysts for fine chemical synthesis has lagged far behind those for bulk chemical process. In recent years metal nanoparticle catalysts have been of great interest in this area due to their unique activity, ease of heterogenization, and robustness. Therefore, metal nanoparticle catalysts are an excellent candidate for the above-mentioned active and robust heterogeneous catalysts and this book provides an overview of this area. The present volume summarizes recent progress on nanoparticle catalysis for various organic transformations from simple redox reactions to complex asymmetric C-C bond forming reactions and also presents seminal studies on new technologies. It comprehensively summarizes advances in metal nanoparticle catalysis across several aspects including reaction manners, mechanistic investigations and new synthetic methodologies to encourage the use of metal nanoparticle catalysts for future organic synthesis. This volume will be of interest to students, researchers and professionals focused on the next-generation of fine chemical synthesis.
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 provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of significant recent developments in the area of metal-ligand cooperativity, with a focus on pincer architectures. The various contributions highlight the widespread impact of M-L co-operativity phenomena on modern organometallic chemistry and catalyst development. The development of efficient and selective catalytic transformations relies on the understanding and fine control of the various elementary reactions that constitutes a catalytic cycle. Co-operative ligands, which actively participate in bond making and bond breaking together to the metal they support, open up new avenues in this area. In particular, buttressing a weak or reactive metal-ligand bond by flanking coordinating arms in a pincer ligand design is proving a versatile strategy to access robust metal complexes that exhibit unusual and selective reactivity patterns. |
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