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To meet the search for new therapeutic compounds this book summarises the research on biologically active organic molecules (chapters 1, 2 and 3), metal complexes with biological activity (chapter 4), and shows the possibilities for co-ordination chemistry in the planning of metal complexes with interesting properties for application (chapters 5, 6, 7, 8, and 9). It should be remembered that in the design of a new potentially active metallodrug, beyond the nature of the metal, the choice of appropriate ligands which affect the thermodynamic and kinetic stability, as well as the solubility and lipophilicity of the complexes is of paramount importance. The information contained in the book concerns: 1) the interactions involving the members of the Nuclear Receptor superfamily and their ligands; 2) the role of chemokine ligands and their receptors in normal and disease processes, and the emerging therapeutic approaches of using chemokine antagonists for appropriately targeted therapy; 3) the inhibition of alkaline phosphatases by calix[4]arenes functionalysed at the macrocyclic upper rim by one or two methylenebisphosphonic acid fragments; 4) the main biological applications, enzyme modelling and antiproliferative and antimicrobial activity of such scorpionate-type complexes, which are classified by ligand and also by transition metal; 5) the silver(I) discrete and polymeric coordination compounds bearing 1,3,5-triaza-7-phosphaadamantane or its derivatives towards engineering functional silver-organic frameworks (MOFs); 6) arylhydrazones of methylene active nitriles and their use as starting materials for the generation of new organic and coordination compounds; 7) amidophosphate ligands as promising sensitisers of lanthanide ions emission; 8) N-acetylsalicylhydrazidate as a versatile ligand for the synthesis of higher nuclearity metal complexes, which are illustrated herein along with their applications; 9) the chemistry and some applications of formazans which can be used for the simultaneous selective determination of several metal cations. All chapters were compiled by renowned scientists, providing both beginners in the field and advanced researchers with comprehensive information on the subject.
Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Complexes of PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of four ruthenium complexes with the polymerizable ligand 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with N,N-bis[2-(diphenylphosphino)ethyl]phenyl-amine (a PNP ligand) have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated.
This book surveys the relatively new area of the synthesis of organic ligands when metal ions act as a template. In the last fifty years this field has undergone an explosive development, marked by a great amount of literature. The material in the book has been arranged according to the type of chemical reaction involved. In this frame, the basic principles of metal template reactions and the shape of the molecules are considered. Designed to satisfy the demands of students, young researchers doing their PhDs, and those working in the field of coordination chemistry, the book details the role of the metal ions and the specific properties of the formed complexes.Metal Mediated Template Synthesis of Ligands offers a comprehensive analysis with wide-ranging references and provides an extensive overview of research on metal-directed organic ligands over the past five decades.
Since hpp*- is known to change electronics at the metal center compared to hpp-, we wanted to investigate if its effects could be examined by spectroscopy. Chapter 5 describes the synthesis of several metal-oxo hpp complexes that were characterized via the M=O IR stretch. The comparison was made between MO(hpp)2L and MO(hpp*)2L [M = W, Re]. The M=O IR stretches were verified by 18O isotopic labeling. Attempts at synthesizing TaOCl3 and TaO(hpp)2L are also detailed. In the last chapter (chapter 6), a few U(hpp) complexes were generated during our development of non-cyclopentadienyl hpp- coordination chemistry of uranium, and are discussed. Two of the complexes characterized via X-ray crystallography are diuranium complexes with UIV-UIV distances of 3.56 Å, possibly being the first compounds with U-U bonds. The new complex U(hpp*)4 is also described.
This reference describes standard and nonstandard coordination modes of ligands in complexes, the intricacies of polyhedron-programmed and regioselective synthesis, and the controlled creation of coordination compounds such as molecular and hn-p-complexes, chelates, and homo- and hetero-nuclear compounds. It offers a clear and concise review of modern synthetic techniques of metal complexes as well as lesser known gas- and solid-phase synthesis, electrosynthesis, and microwave and ultrasonic treatment of the reaction system. The authors pay special attention to o-hydroxyazomethines and their S-, Se-containing analogues, b-diketones, and quinines, among others, and examine the immediate interaction of ligands and metal salts or carbonyls.
This, the second and final volume of Reactions of Coordinated Ligands, describes the chemistry of ligands bound through non-carbon atoms, and of coordinated carbon dioxide. As before, emphasis is on the underlying mechanisms, which provide a unity of understanding for superficially disparate processes. The wide range of topics covered illustrates well both the versatility and the usefulness of coordination chemistry in the controlled activation of ligands. Looking to the future, carbon dioxide is the feedstock of last resort. The homogeneous reduction of dinitrogen to ammonia now seems unlikely to replace the Haber process, but solution reactions also lead to more complex, varied, and valuable products. Nitrogen monoxide, a "non innocent" ligand, impinges as pollutant and reagent. Its rich chemistry stems from its linked roles as three-electron donor, and as extremely powerful -acceptor. In the hydrolysis and condensation of complexed amides, esters etc. , metals act both as templates and as tunable and poly functional Lewis acids. Here the control of hydrophobic and steric interactions begins to model the subtle mechanisms of biological specificity. Finally, phosphorus and sulfur are imporant both as ligand atoms in themselves, and as anchors for other functionalities. I would like to thank all those who have been involved in the writing and production of this work, and also my colleagues old and new, at Glasgow and the University of North Texas, for their support. Paul S. Braterman v CONTENTS 1. Reactions of Coordinated Carbon Dioxide 1 J. D. Miller 1.