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Metal N-heterocyclic carbene (NHC) complexes have recently gained much popularity due to their tunable, steric, and electronic properties. Applications for such versatile molecules include organocatalysis1 2 3, olefin metathesis4 5 6, sundry cyclization reactions7 8 9, and materials chemistry10 11. Redox active NHCs are of special interest due to their ability to alter the electronic properties of the metal centers they are ligated to.12 In the first chapter, Au(I)-NHC complexes were synthesized and tested for biological activity in human cancer cell lines. Increasing reactive oxygen species (ROS) in cellular systems has proven to be a successful pathway for treating cancer13 14 15. The redox active group in this case was naphthoquinone which contributed to the oxidative stress applied to the tumor cells. Three Au(I)-NHC complexes were synthesized and analyzed structurally utilizing 1H NMR, 13C NMR, and X-ray crystallography. Biological studies including IC50 cell culture lines and cell proliferation analyses were performed to determine the complexes' efficiency and success as a cancer treatment drug. The second chapter describes a theoretical approach to synthesize a redox active tetrathiafulvalene (TTF) fused with an iridium-NHC complex to serve as a redox switchable catalyst. The first compound in this synthetic route was successfully synthesized and analyzed structurally with 1H and 13C NMR, UV-Vis spectroscopy, and IR spectroscopy. The electrochemical properties were also investigated. Tetrathiafulvalene possesses the ability to undergo multiple one electron reversible redox transformations. This unique characteristic paired with the catalytic properties of iridium-NHC could produce a catalyst capable of accessing three or more catalytic species based upon the oxidation state of TTF.
Redox-Active Ligands Authoritative resource showcasing a new family of ligands that can lead to better catalysts and promising applications in organic synthesis Redox-Active Ligands gives a comprehensive overview of the unique features of redox-active ligands, describing their structure and synthesis, the characterization of their coordination complexes, and important applications in homogeneous catalysis. The work reflects the diversity of the subject by including ongoing research spanning coordination chemistry, organometallic chemistry, bioinspired catalysis, proton and electron transfer, and the ability of such ligands to interact with early and late transition metals, lanthanides, and actinides. The book is divided into three parts, devoted to introduction and concepts, applications, and case studies. After the introduction on key concepts related to the field, and the different types of ligands and complexes in which ligand-centered redox activity is commonly observed, mechanistic and computational studies are described. The second part focuses on catalytic applications of redox-active complexes, including examples from radical transformations, coordination chemistry and organic synthesis. Finally, case studies of redox-active guanidine ligands, and of lanthanides and actinides are presented. Other specific sample topics covered include: An overview of the electronic features of redox-active ligands, covering their historical perspective and biological background The versatility and mode of action of redox-active ligands, which sets them apart from more classic and tunable ligands such as phosphines or N-heterocyclic carbenes Preparation and catalytic applications of complexes of stable N-aryl radicals Metal complexes with redox-active ligands in H+/e- transfer transformations By providing up-to-date information on important concepts and applications, Redox-Active Ligands is an essential reading for researchers working in organometallic and coordination chemistry, catalysis, organic synthesis, and (bio)inorganic chemistry, as well as newcomers to the field.
This book presents a comprehensive introduction to the unique and fundamental features of redox-active ligands, the preparation and characterization of their coordination complexes, and finally the importance of this class of molecules to biology, catalysis and materials. The book aims to provide a broadly accessible introduction to the particular features and opportunities unique to redox-active ligands. It begins with an introduction to the intellectual challenges posed by redox-active ligands and descriptions of the types of ligands and complexes in which ligand-centered redox activity are commonly observed. Following this, the book is divided into two sections as follows: The first section focuses on electronic structure and bonding, which has historically dominated this field and continues to be actively researched. The spectroscopic and other physical measurements that have been used to elucidate the electronic structure of these compounds are described. The interplay between synthesis, bonding models, and physical measurements has often been critical in shaping our understanding of these compounds. This interplay is illustrated by a number of case studies. The second section focuses on the use of redox-active complexes in stoichiometric and catalytic reactions. The scope of known reactions is presented, including examples from bioinorganic chemistry (both enzymes and model compounds). Where possible, the significance of the redox-active ligand is discussed, with an eye both to summarizing existing knowledge and pointing out possibilities for future research. This book explains the underpinnings of physical and theoretical techniques of redox-active ligands, providing up to date information on definitions, scope and applications for research scientists and graduate students working in organic and inorganic chemistry, organometallics and coordination chemistry.
It has long been recognized that metal spin states play a central role in the reactivity of important biomolecules, in industrial catalysis and in spin crossover compounds. As the fields of inorganic chemistry and catalysis move towards the use of cheap, non-toxic first row transition metals, it is essential to understand the important role of spin states in influencing molecular structure, bonding and reactivity. Spin States in Biochemistry and Inorganic Chemistry provides a complete picture on the importance of spin states for reactivity in biochemistry and inorganic chemistry, presenting both theoretical and experimental perspectives. The successes and pitfalls of theoretical methods such as DFT, ligand-field theory and coupled cluster theory are discussed, and these methods are applied in studies throughout the book. Important spectroscopic techniques to determine spin states in transition metal complexes and proteins are explained, and the use of NMR for the analysis of spin densities is described. Topics covered include: DFT and ab initio wavefunction approaches to spin states Experimental techniques for determining spin states Molecular discovery in spin crossover Multiple spin state scenarios in organometallic reactivity and gas phase reactions Transition-metal complexes involving redox non-innocent ligands Polynuclear iron sulfur clusters Molecular magnetism NMR analysis of spin densities This book is a valuable reference for researchers working in bioinorganic and inorganic chemistry, computational chemistry, organometallic chemistry, catalysis, spin-crossover materials, materials science, biophysics and pharmaceutical chemistry.
Vanadium is one of the more abundant elements in the Earth’s crust and exhibits a wide range of oxidation states in its compounds making it potentially a more sustainable and more economical choice as a catalyst than the noble metals. A wide variety of reactions have been found to be catalysed by homogeneous, supported and heterogeneous vanadium complexes and the number of applications is growing fast. Bringing together the research on the catalytic uses of this element into one essential resource, including theoretical perspectives on proposed mechanisms for vanadium catalysis and an overview of its relevance in biological processes, this book is a useful reference for industrial and academic chemists alike.
Authored by one of the world's leading experts in the field, this treatment of a core topic in coordination chemistry discusses the fundamentals, including the physical properties and chemical reactivity, followed by interesting applications in catalysis and biochemistry. The result is a perfect overview for all newcomers to the field as well as more experienced researchers.
An expert overview of current research, applications, and economic and environmental advantages The study and development of new homogeneous catalysts based on first-row metals (Mn, Fe, Co, Ni, and Cu) has grown significantly due to the economic and environmental advantages that non-noble metals present. Base metals offer reduced cost, greater supply, and lower toxicity levels than noble metals?enabling greater opportunity for scientific investigation and increased development of practical applications. Non-Noble Metal Catalysis provides an authoritative survey of the field, from fundamental concepts and computational methods to industrial applications and reaction classes. Recognized experts in organometallic chemistry and homogeneous catalysis, the authors present a comprehensive overview of the conceptual and practical aspects of non-noble metal catalysts. Examination of topics including non-innocent ligands, proton-coupled electron transfer, and multi-nuclear complexes provide essential background information, while areas such as kinetic lability and lifetimes of intermediates reflect current research and shifting trends in the field. This timely book demonstrates the efficacy of base metal catalysts in the pharmaceutical, fine-chemical, and agrochemical industries, addressing both environmental and economic concerns. Providing essential conceptual and practical exploration, this valuable resource: -Illustrates how unravelling new reactivity patterns can lead to new catalysts and new applications -Highlights the multiple advantages of using non-noble metals in homogenous catalysis -Demonstrates how the availability of non-noble metal catalysis reduces costs and leads to immense savings for the chemical industry -Reveals how non-noble metal catalysis are more sustainable than noble metals such as palladium or platinum Non-Noble Metal Catalysis: Molecular Approaches and Reactions is an indispensable source of up-to-date information for catalytic chemists, organic chemists, industrial chemists, organometallic chemists, and those seeking to broaden their knowledge of catalytic chemistry.
Advances in Organometallic Chemistry, Volume 73, the latest release in this longstanding serial, is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. It is ideal for a wide range of researchers involved in organometallic chemistry, including synthetic protocols, mechanistic studies and practical applications. Specific chapters in this new release include Metal carbonyl promoted multicomponent coupling of alkyne for synthesis of heterocyclic compounds, Group 10 metal(0) complexes stabilized by phosphorus and carbon donor ligands, Synthesis of Nitrogen-containing Molecules via Transition Metal-Catalyzed Reactions on Isoxazoles, Anthraniils and Benzoisoxazoles, and more. Contains contributions from leading authorities in the field of organometallic chemistry Covers topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more Informs and updates readers on the latest developments in the field Carefully edited to provide easy-to-read material
Transition metal complexes incorporating redox-active ligands have the potential to facilitate controlled multielectron chemistry, enabling their use in catalysis and energy storage applications. Moreover, the use of transition metal complexes containing redox-active ligands has been extended to two- (2D) and three-dimensional (3D) materials, such as supramolecular assemblies (i.e., metallacycles, molecular cages, or macrocycles) and metal-organic frameworks (MOFs) for catalytic, magnetic, electronic, and sensing applications. Salens (N2O2 bis(Schiff-base)-bis(phenolate) are an important class of redox-active ligands, and have been investigated in detail as they are able to stabilize both low and high metal oxidation states for the above-mentioned applications. The work in this thesis focuses on the synthesis and electronic structure elucidation of metal salen complexes in monomeric form, as discrete supramolecular assemblies and 3D MOFs. Structural and spectroscopic characterization of the neutral and oxidized species was completed using mass spectrometry, cyclic voltammetry, X-ray diffraction, NMR, UV-Vis-NIR, and EPR spectroscopies, as well as theoretical (DFT) calculations. Chapter 2 discusses the synthesis and electronic structure evaluation of a series of oxidized uranyl complexes, containing redox-active salen ligands with varying para-ring substituents (tBu, OMe, NMe2). Chapters 3 and 4 discuss the incorporation of a redox-active nickel salen complex equipped with pyridyl groups on the peripheral positions of the ligand framework into supramolecular structures via coordination-driven self-assembly. The self-assembly results in formation of a number of distinct metallacycles, affording di-, tetra-, and octa-ligand radical species. Finally, the design, synthesis, and incorporation of metal salen units into MOFs is discussed in Chapter 5. Preliminary assembly and oxidation experiments are presented as an opportunity to explore the redox-properties of salen complexes incorporated into a solid-state 3D framework. Overall, the work described in this thesis provides a pathway for salen ligand radical systems to be used in redox-controlled host-guest chemistry, catalysis, and sensing.