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This book will describe Ruthenium complexes as chemotherapeutic agent specifically at tumor site. It has been the most challenging task in the area of cancer therapy. Nanoparticles are now emerging as the most effective alternative to traditional chemotherapeutic approach. Nanoparticles have been shown to be useful in this respect. However, in view of organ system complicacies, instead of using nanoparticles as a delivery tool, it will be more appropriate to synthesize a drug of nanoparticle size that can use blood transport mechanism to reach the tumor site and regress cancer. Due to less toxicity and effective bio-distribution, ruthenium (Ru) complexes are of much current interest. Additionally, lumiscent Ru-complexes can be synthesized in nanoparticle size and can be directly traced at tissue level. The book will contain the synthesis, characterization, and applications of various Ruthenium complexes as chemotherapeutic agents. The book will also cover the introduction to chemotherapy, classification of Ru- complexes with respect to their oxidation states and geometry, Ruthenium complexes of nano size: shape and binding- selectivity, binding of ruthenium complexes with DNA, DNA cleavage studies and cytotoxicity. The present book will be more beneficial to researchers, scientists and biomedical. Current book will empower specially to younger generation to create a new world of ruthenium chemistry in material science as well as in medicines. This book will be also beneficial to national/international research laboratories, and academia with interest in the area of coordination chemistry more especially to the Ruthenium compounds and its applications.
Mixed valency in a ligand bridged homo-polynuclear complex arises when metal centers exist in their different oxidation states. The extent of intermetallic electronic coupling in the mixed valent state of polynuclear complex varies primarily depending on the nature of bridging and ancillary ligands as well as on the metal ion. On the other hand, the use of redox active (redox non-innocent) ligands in the complex framework creates ambiguities in the assignment of valence and spin configurations of such complexes as both the metal and ligand centers can take part in electron transfer processes. In consequence precise determination of valence and spin distributions in transition metal complexes comprising of redox non-innocent ligands is considered to be a formidable challenge. Thus, this book has been focused on how to overcome such problems through the correlation of experimental and theoretical results.
Edited by a team of highly respected researchers combining their expertise in chemistry, physics, and medicine, this book focuses on the use of rutheniumcontaining complexes in artificial photosynthesis and medicine. Following a brief introduction to the basic coordination chemistry of ruthenium complexes and their synthesis in section one, as well as their photophysical and photochemical properties, the authors discuss in detail the major concepts of artificial photosynthesis and mechanisms of hydrogen production and water oxidation with ruthenium in section two. The third section of the text covers biological properties and important medical applications of ruthenium complexes as therapeutic agents or in diagnostic imaging. Aimed at stimulating research in this active field, this is an invaluable information source for researchers in academia, health research institutes and governmental departments working in the field of organometallic chemistry, green and sustainable chemistry as well as medicine/drug discovery, while equally serving as a useful reference also for scientists in industry.
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.
The investigation and development of transition metal complexes as cancer chemotherapeutics has gained a lot of interest in the past few decades and has become a promising area of research. Metal complexes of platinum and ruthenium in particular that have demonstrated success as anticancer drugs or are under exploration currently for clinical use are highlighted in Chapter 1. Chapter 2 describes studies undertaken to understand the neurotoxicity of ruthenium(II) polypyridyl complexes (RPCs), including toxicity in mice and inhibition of the enzyme acetylcholinesterase (AChE), as previous work by Dwyer demonstrated that RPCs could be acutely toxic in mice, presumably due to their inhibition of AChE. Several ruthenium complexes were screened for their enzyme inhibitory potency which was correlated to their structural properties including size, charge, and lipophilicity. In addition, the inhibitory activity of the compounds was correlated to their animal toxicity data so as to understand the potential mode of action of the RPCs in vivo. Chapter 3 describes the synthesis of a series of novel ruthenium(II) polypyridyl complexes and their characterization. These complexes were prepared in an effort to tune the reduction potential of the redox-active intercalating ligand (RAIL) to potentials slightly above and below those observed for the Ru-tatpp complexes. The redox activity of ruthenium-tatpp complexes appears to be responsible for their DNA cleavage activity and these analogues, with slightly different reduction potentials, should give us additional insight into the activity of this class of RPCs. In Chapter 4, the electrochemical properties of the RPCs were measured and correlated with their ability to cause DNA cleavage under reducing conditions with GSH. Complexes with reduction potentials less (more positive) than the redox couple of GSH/GSSG were shown to efficiently cleave DNA. However complexes with higher reduction potentials than the biological reducing agent were not observed to cleave DNA under the same conditions. Cytotoxicity screening of these complexes in human non-small cell lung carcinoma cell lines (NSCLC -- H358 and HOP-62) and breast adenocarcinoma cell line (MCF-7), as well as the non-malignant cell line (MCF-10) was performed and described in Chapter 4.
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.
This dissertation describes the synthesis and reactivity of tantalum metal complexes containing a tridentate redox-active ligand. Fundamental studies have focused on utilizing the redox-active ligand to store multiple electron equivalents for oxidative addition and reductive elimination reactions. Chapter 1 provides an introduction to the characteristics of redox-active ligands and provides an overview of group transfer reactions involving redox-active ligands. The previous published results of bidentate redox-active ligands coordinated to Group IV d0 metals are discussed in terms of their decomposition side reactions. Chapter 2 describes the coordination of a known tridentate redox-active bis(phenoxy)amide ligand, (ONO), to a d0 tantalum(V) metal center and the examination of the redox properties of the resulting chloro oxidation products by electrochemical and spectroscopic methods. Chapter 3 examines the reactivity of the (ONO)TaR2 complexes in the general context of organometallic chemistry with a focus on protonolysis and reactivity with aryl azides, a known source of nitrene fragments upon oxidation. Chapter 4 examines the reactivity of the (ONO)TaX2 (X = Me, Cl) compounds with bulky diazoalkanes, a known carbene transfer reagent. The (ONO)TaCl2 complex proved to be a competent catalyst to generate cyclopropanes from styrene and the corresponding diazoalkane. Chapter 5 explores the utilization of the (ONO) ligand to store electron equivalents for the catalytic nitrene-nitrene coupling reactions with organoazides to afford organodiazenes. Finally, Chapter 6 addresses the electronic considerations of a related redox-active triamido ligand in an effort to tune the ligand's redox potentials.
The Chemistry of Ruthenium is concerned with the chemistry of ruthenium, with emphasis on synthesis and structure. The discussion spans a wide range of fields, from coordination chemistry and organometallic chemistry to structural chemistry (of both molecular and extended lattices), electrochemistry and photochemistry, as well as kinetics and spectroscopy. Comprised of 15 chapters, this book begins with an introduction to the discovery and early history of ruthenium, along with its extraction and purification, isotopes, physical and chemical properties, and applications. The discussion then turns to the concept of oxidation state and a scheme for systematizing descriptive inorganic chemistry together with its applicability to ruthenium chemistry. Subsequent chapters focus on the chemistry of ruthenium(VIII), ruthenium(VII), ruthenium(VI), ruthenium(V), ruthenium(IV), ruthenium(III), ruthenium(II), ruthenium(I), and ruthenium(0). The book also considers ruthenium carbonyl clusters and nitrosyls before concluding with a review of the photophysics and photochemistry of tris(diimine)ruthenium(II) complexes. This monograph will be useful to students, practitioners, and researchers in the field of inorganic chemistry, as well as those who are interested in the chemistry of ruthenium.
Three redox series of complexes of the general formula Ru(II) (bpy) 2LL an Ru(II) (Py)4LL (bpy=2,2'-bipyridine) are reported, where LL are the ligands, 1,2-dihydroxybenzen, 2-aminophenol or 1,2-diaminobenzene. These ligands can exist in the fully reduced catechol form, or the one and two electron oxidized semiquinone and quinone forms. Electronic and electron spin resonance spectroscopic, and electrochemical data are discussed in terms of orbital mixing and electronic structure, and the number of oxygen or nitrogen atoms in the coordinating ligand.