Download or read book Development of Polypyridyl Pyrazolate bridging Dinucleating Ligands Containing Hydrogen bond Donors written by Kwanyi Ng and published by . This book was released on 2012 with total page 171 pages. Available in PDF, EPUB and Kindle. Book excerpt: The first chapter of this dissertation describes the importance of hydrogen bonding (H-bonding) within the secondary coordination sphere of metal complexes. Particular emphasis is given to the correlations between the structures of metalloenzyme actives and their functions. Classical examples of synthetic metal complexes, which are designed to mimic some of the features of metalloenzyme active sites, are also reviewed. The detection of reactive intermediates in the mononuclear systems has inspired the development of the dinucleating ligands, which is the cornerstone of the work described in this dissertation. In Chapter 2, the synthesis of a (carboxyamido)pyridinepyrazolate (H5bppap) dinucleating ligand is described. Bimetallic iron and cobalt complexes of H5bppap ([MII2H2bppap]+) showed structural differences in both their primary and secondary coordination spheres. The [CoII2H2bppap]+ is 5,5-corodinate while [FeII2H2bppap]+ is 5,6-coordinate. The binding of small molecules into the preorganized ligand cavity is verified by the hydration of [FeII2H2bppap]+ and [CoII2H2bppap]+, leading to the formation of complexes [{CoII(OH)}CoIIH3bppap]+ and [{FeII(OH)}FeIIH3bppap]+, in which only one of the metal centers has a terminal hydroxo ligand. Chapter 3 will present the synthesis and characterization of a dimanganese(II) complex, [MnII2H2bppap]+. The coordination chemistry of the dimanganese(II) analog of H5bppap is considerably different from its iron and cobalt counterparts. The insertion of external ligands into [MnII2H2bppap]+ with simultaneous protonation of the ligand backbone led to the isolation of a series of seven-coordinate dinuclear MnII species, [MnII2([mu]61549;-X)H4bppap]2+. Chapter 4 illustrates the design and synthesis of a dinucleating ligand, 3,5-Bis[bis(N-6-neopentylamino-2-pyridylmethyl)aminomethyl]-1H-pyrazole (H5bnppap). The syntheses and characterization of the corresponding dinuclear bis(hydroxo) complexes, [MII2H4bnppap(OH)2]+ are discussed. These complexes feature the rare terminal bis(OH) moiety within one molecular unit with the MII-OH units are positioned in a syn-configuration, placing the hydroxo ligands in close proximity (ca. 3 Å apart), which may be a prerequisite for water oxidation. The second part of the chapter describes the hydrolytic studies utilizing [CoII2H4bnppap(OH)2]+. Both [CoII2H4bnppap(OH)2]+ and [{CoII (OH)}MIIH3bppap]+ are able to hydrolyze carbon dioxide to give carbonate-bridged complexes. However, only [CoII2H4bnppap(OH)2]+ is able to hydrolyze triphenylborane to triphenylborate. These results indicate that control of the number of hydroxide ligands within the bimetallic cavity could be used as a strategy to regulate activity of metal-hydroxo complexes.
Download or read book Dissertation Abstracts International written by and published by . This book was released on 2007 with total page 924 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Inorganic Syntheses Volume 32 written by and published by John Wiley & Sons. This book was released on 2009-09-22 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: The Inorganic Synthesis Series provides all users of inorganic substances with detailed and foolproof procedures for the preparation of important and timely compounds. This new volume includes information on water-solubilizing ligands for organometallics, labile ligand complexes, and the syntheses of cluster compounds and hydrides.
Download or read book Molecular Water Oxidation Catalysis written by Antoni Llobet and published by John Wiley & Sons. This book was released on 2014-04-14 with total page 343 pages. Available in PDF, EPUB and Kindle. Book excerpt: Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evolving system of photosystem II and the heme chlorite-dismutase. This book is a valuable resource for researchers working on water oxidation catalysis, solar energy conversion and artificial photosynthesis, as well as for chemists and materials scientists with a broad interest in new sustainable energy conversion schemes.
Download or read book Photo and Electro Catalytic Processes written by Jianmin Ma and published by John Wiley & Sons. This book was released on 2022-01-25 with total page 596 pages. Available in PDF, EPUB and Kindle. Book excerpt: Explore green catalytic reactions with this reference from a renowned leader in the field Green reactions—like photo-, photoelectro-, and electro-catalytic reactions—offer viable technologies to solve difficult problems without significant damage to the environment. In particular, some gas-involved reactions are especially useful in the creation of liquid fuels and cost-effective products. In Photo- and Electro-Catalytic Processes: Water Splitting, N2 Fixing, CO2 Reduction, award-winning researcher Jianmin Ma delivers a comprehensive overview of photo-, electro-, and photoelectron-catalysts in a variety of processes, including O2 reduction, CO2 reduction, N2 reduction, H2 production, water oxidation, oxygen evolution, and hydrogen evolution. The book offers detailed information on the underlying mechanisms, costs, and synthetic methods of catalysts. Filled with authoritative and critical information on green catalytic processes that promise to answer many of our most pressing energy and environmental questions, this book also includes: Thorough introductions to electrocatalytic oxygen reduction and evolution reactions, as well as electrocatalytic hydrogen evolution reactions Comprehensive explorations of electrocatalytic water splitting, CO2 reduction, and N2 reduction Practical discussions of photoelectrocatalytic H2 production, water splitting, and CO2 reduction In-depth examinations of photoelectrochemical oxygen evolution and nitrogen reduction Perfect for catalytic chemists and photochemists, Photo- and Electro-Catalytic Processes: Water Splitting, N2 Fixing, CO2 Reduction also belongs in the libraries of materials scientists and inorganic chemists seeking a one-stop resource on the novel aspects of photo-, electro-, and photoelectro-catalytic reactions.
Download or read book The Chemoselective Catalytic Oxidation of Alcohols Diols and Polyols to Ketones and Hydroxyketones written by Ronald Michael Painter and published by Stanford University. This book was released on 2011 with total page 110 pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemoselective oxidation of vicinal diols to α-hydroxyketones is a challenge in organic syntheses because not only does the diol need to be oxidized selectively to a monocarbonyl compound, but diols are also prone to overoxidation and oxidative cleavage. Employing a cationic palladium complex, [(neocuproine)Pd(OAc)]2(OTf)2, we were able to demonstrate the selective oxidation of glycerol to dihydroxyacetone mediated by either benzoquinone or O2 as the terminal oxidant, an accomplishment that has little precedent in homogeneous catalysis. Mechanistic studies were undertaken to uncover the nature of this remarkable chemoselectivity. Kinetic and deuterium-labeling studies implicate reversible β-hydride elimination from isomeric Pd alkoxides and turnover-limiting displacement of the dihydroxyacetone product by benzoquinone. We successfully extended this methodology to other terminal 1,2-diols and symmetric vicinal 1,2-diols and have carried out aerobic oxidation of these substrates catalyzed by 1. Examination of the reactivity of 1 with conformationally-restricted 1,2-cyclohexanediols suggests that the diol must chelate to the Pd center for effective oxidation to the hydroxyketone product. In a separate project, we have also investigated the electrocatalytic reduction of dioxygen by several dinuclear copper complexes, an important reaction for fuel cell applications.
Download or read book Trends in Organometallic Chemistry written by and published by . This book was released on 1999 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Multi copper Oxidases written by Albrecht Messerschmidt and published by World Scientific. This book was released on 1997 with total page 477 pages. Available in PDF, EPUB and Kindle. Book excerpt: The biological activation of dioxygen is a key reaction in biological systems. Enzymes involved in direct oxygen activation are oxidases and oxygenases. Multi-copper oxidases are an important class of oxidases reducing dioxygen in a four-electron reduction to water with concomitant one-electron oxidation of the reducing substrate. The progress in the characterization and understanding of the structure and function of these enzymes has advanced so tremendously over the last ten years that the publication of a book documenting these achievements has been overdue.Especially the recent discovery of a key role of the FET3 protein of Saccharomyces cerevisae, a multi-copper oxidase, in iron metabolism of this eukaryote has underpinned the function of the plasma multi-copper oxidase ceruloplasmin in vetebrate iron transport. The lately determined x-ray structure of human ceruloplasmin confirms its close structural relatedness to the plant multi-copper oxidases ascorbate oxidase and laccase and due to strong amino-acid sequence similarities has allowed to construct a useful model of the more distantly related blood-clotting factor VIII.This book contains review articles from experts in the field, dealing with modern spectroscopy, enzyme kinetics, bioinorganic chemistry, x-ray crystallography, electron transfer reactions, molecular biology, medical aspects and potential industrial applications of the three main members of multi-copper oxidases, i.e., laccase, ascorbate oxidase and ceruloplasmin.
Download or read book Essentials of Computational Chemistry written by Christopher J. Cramer and published by John Wiley & Sons. This book was released on 2013-04-29 with total page 624 pages. Available in PDF, EPUB and Kindle. Book excerpt: Essentials of Computational Chemistry provides a balanced introduction to this dynamic subject. Suitable for both experimentalists and theorists, a wide range of samples and applications are included drawn from all key areas. The book carefully leads the reader thorough the necessary equations providing information explanations and reasoning where necessary and firmly placing each equation in context.
Download or read book Energy Resources through Photochemistry and Catalysis written by Michael Gratzel and published by Elsevier. This book was released on 2012-12-02 with total page 588 pages. Available in PDF, EPUB and Kindle. Book excerpt: Energy Resources through Photochemistry and Catalysis reviews the state of the art in the development of energy conversion devices based on catalytic and photochemical reactions. The focus is on catalysis of redox reactions and their application to the photocleavage of water, reduction of carbon dioxide, and fixation of nitrogen. Some fundamental aspects of catalysis as it relates to processes of light energy harvesting and charge separation in photochemical or photoelectrochemical conversion systems are also discussed. This monograph is comprised of 16 chapters covering light-induced redox reactions and reaction dynamics in organized assemblies such as micelles, colloidal metals, or semiconductors, together with strategies for molecular engineering of artificial photosynthetic devices. The principles of electrochemical conversion of light energy via semiconductor electrodes or semiconducting particles are also considered. Furthermore, thermodynamic characteristics for some reactions that can be utilized for storage of solar energy in the form of chemical energy are examined. The remaining chapters look at the role of porphyrins in natural and artificial photosynthesis; the use of semiconductor powders and particulate systems for photocatalysis and photosynthesis; and hydrogen-generating solar cells based on platinum-group metal activated photocathodes. This text will be a useful resource for scientists and policymakers concerned with finding alternative sources of energy.
Download or read book AB INITIO Molecular Orbital Theory written by Warren J. Hehre and published by Wiley-Interscience. This book was released on 1986-03-24 with total page 572 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book addresses the formulation of theoretical molecular orbital models starting from quantum mechanics, and compares them to experimental results. It draws on a series of models that have already received widespread application and are available for new applications.
Download or read book Comprehensive Coordination Chemistry II written by J. A. McCleverty and published by Newnes. This book was released on 2003-12-03 with total page 11845 pages. Available in PDF, EPUB and Kindle. Book excerpt: Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest.
Download or read book The F Elements written by Nikolas Kaltsoyannis and published by . This book was released on 1999 with total page 104 pages. Available in PDF, EPUB and Kindle. Book excerpt: The lanthanides and actinides (the f elements) are rarely studied in detail by chemistry undergraduates. More often they appear as an afterthought in bonding, spectroscopy, magnetism, coordination chemistry, and organometallics courses. This is largely because of a lack of an accessible text treating the chemistry of these elements in one cover. Moreover, the placement of lanthanides and actinides in the closing pages of standard inorganic chemistry text books serves to marginalise these elements further. The f elements has therefore been written to fill a gap in the undergraduate chemistry textbook market. It covers much of the fundamental chemistry of the lanthanide and actinide elements, including coordination chemistry, solid state compounds, organometallic chemistry, electronic spectroscopy, and magnetism. Many comparisons are made between the chemistry of the lanthanides and actinides and that of the transition elements, which is generally much more familiar to undergraduate chemistry students. The book uses the chemistry of the f elements as a vehicle for the communication of several important chemical concepts that are not usually discussed in detail in undergraduate courses, for example the chemical consequences of relativity and the lanthanide and actinide contractions. Many important modern applications of f element chemistry, e.g. the use of actinides in nuclear power generation and of the lanthanides in magnetic resonance imaging and catalytic converters in motor vehicle exhausts, are also discussed in depth.
Download or read book Nickel and Its Surprising Impact in Nature written by Astrid Sigel and published by John Wiley & Sons. This book was released on 2007-03-13 with total page 728 pages. Available in PDF, EPUB and Kindle. Book excerpt: Helmut Sigel, Astrid Sigel and Roland K.O. Sigel, in close cooperation with John Wiley & Sons, launch a new Series “Metal Ions in Life Sciences”. The philosophy of the Series is based on the one successfully applied to a previous series published by another publisher, but the move from “biological systems” to “life sciences” will open the aims and scope and allow for the publication of books touching on the interface between chemistry, biology, pharmacology, biochemistry and medicine. Volume 2 focuses on the vibrant research area concerning nickel as well as its complexes and their role in Nature. With more than 2,800 references and over 130 illustrations, it is an essential resource for scientists working in the wide range from inorganic biochemistry all the way through to medicine. In 17 stimulating chapters, written by 47 internationally recognized experts, Nickel and Its Surprising Impact in Nature highlights critically the biogeochemistry of nickel, its role in the environment, in plants and cyanobacteria, as well as for the gastric pathogen Helicobacter pylori, for gene expression and carcinogenensis. In addition, it covers the complex-forming properties of nickel with amino acids, peptides, phosphates, nucleotides, and nucleic acids. The volume also provides sophisticated insights in the recent progress made in understanding the role of nickel in enzymes such as ureases, hydrogenases, superoxide dismutases, acireductone dioxygenases, acetyl-coenzyme A synthases, carbon monoxide dehydrogenases, methyl-coenzyme M reductases...and it reveals the chaperones of nickel metabolism.
Download or read book The Manipulation of Air Sensitive Compounds written by Duward F. Shriver and published by John Wiley & Sons. This book was released on 1986-11-05 with total page 340 pages. Available in PDF, EPUB and Kindle. Book excerpt: Revised to reflect the continuing and growing importance of research and development within this field, The Manipulation of Air-Sensitive Compounds, 2nd Edition offers state-of-the-art methods used in handling air-sensitive compounds, including gases. Part One covers inert atmosphere techniques, while Part Two treats vacuum line techniques. Appendixes provide safety data, information on materials used to construct apparatus, and a table of vapor pressures of common volatile substances.
Download or read book Comprehensive Organometallic Chemistry II written by Richard J. Puddephatt and published by Elsevier. This book was released on 1995 with total page 670 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Alkane C H Activation by Single Site Metal Catalysis written by Pedro J. Pérez and published by Springer Science & Business Media. This book was released on 2012-09-15 with total page 277 pages. Available in PDF, EPUB and Kindle. Book excerpt: Over the past decade, much research effort has been devoted to the design and synthesis of new reagents and catalysts that can influence carbon-hydrogen bond activation, mainly because of the prospect that C−H activation could enable the conversion of cheap and abundant alkanes into valuable functionalized organic compounds. Alkane C-H Activation by Single-Site Metal Catalysis presents the current state-of-the-art development in the catalytic systems for the catalytic trans-formations of alkanes under homogeneous conditions. Chapter 1 offers a comprehensive summary of the main discoveries realized so far. Chapter 2 reviews the so-called electrophilic activation, initiated by Shulpín in the late 60s, and the base for the Catalytica system. Chapter 3 examines the catalytic borylation of alkanes, discovered by Hartwig, whereas chapter 4 provides an updated vision of the alkane dehydrogenation reaction. Chapter 5 covers the oxygenation of C-H bonds, a field of enormous interest with bioinorganic im-plications, and finally chapter 6 presents the functionalization of alkane C-H bonds by carbene or nitrene insertion. The history of C-H bond activation, and the current research described in this book, highlight the current research and present the reader with an outlook of this field which continues to be explored by an increasingly visionary and enthusiastic group of organic, organometallic, biological and physical chemists.
