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Author : Boris Kosog
Publisher :
ISBN 13 :
Total Pages : 228 pages
Book Rating : 4.:/5 (823 download)
Download or read book Ligand Influences on Properties of Uranium Coordination Complexes written by Boris Kosog and published by . This book was released on 2012 with total page 228 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Shinichi Kawaguchi
Publisher : Springer Science & Business Media
ISBN 13 : 3642501486
Total Pages : 129 pages
Book Rating : 4.6/5 (425 download)
Download or read book Variety in Coordination Modes of Ligands in Metal Complexes written by Shinichi Kawaguchi and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 129 pages. Available in PDF, EPUB and Kindle. Book excerpt: Metal complexes play important roles as catalysts or other participants in synthetic and biological reactions. Substrates and sometimes attacking reagents also are activated through coordination with metal atoms or ions. In these events the natures not only of the central metals but also of ancillary ligands exert important influences on the stability and reactivity of the coordinated substrates. A ligand in general can adopt various coordination modes depending on its chemical environment, thus functioning as a probe. The number of coordination modes increases with increasing complexity of the ligand. In this book it is shown that even the simplest mono- and diatomic ligands such as H, CO, and N2 exhibit a variety of coordination modes, which are related to their reactions. The thiocyanate anion is taken up as a representative of the triatomic ambidentate ligands, and factors influencing the preferences for N- und S-bonding are summarized. Coordination chemistry of ß-dicarbonyl compounds is a highlight of this book. Acetylacetone, one of the most familiar Werner ligands, is shown to favor -carbon and n-allylic bonding in many instances. Its versatile behaviour in changing coordination modes is revealed.
Author : Oanh Phi Lam
Publisher :
ISBN 13 : 9781124126425
Total Pages : 584 pages
Book Rating : 4.1/5 (264 download)
Download or read book Control of Structure and Reactivity by Ligand Design written by Oanh Phi Lam and published by . This book was released on 2010 with total page 584 pages. Available in PDF, EPUB and Kindle. Book excerpt: The ability of uranium to support multiple oxidation states, achieve various coordination numbers combined with the highly reducing nature of the U(III) ion makes this metal a great candidate for small molecule activation. The challenge lies in designing the appropriate ligand that can stabilize a highly reactive uranium center while simultaneously promoting activation and functionalization of small molecules in a controlled manner. Presented herein are the syntheses of two new ligand systems for uranium coordination chemistry. The effects of different ligand environments on the reactivity of trivalent uranium complexes toward small molecules are investigated. The U(III) complexes containing triazacylononane tris-aryloxide ligands [((R/ArO)3/tacn)U] (R = t-Bu, Ad) were found to stabilize charge-separated species with radical anionic ligands. Isolation of uranium ketyl radical complex, [((t-Bu/ArO3/tacn)UIV(OC*t-Bu/Ph2)], was achieved through a one-electron reduction of di-tert-butyl benzophenone with [((t-Bu/ArO3/tacn)U]. One-electron reduction of diphenyldiazomethane by [((Ad/ArO)3/tacn)U] generated a highly reactive charge-separated intermediate species [(([((Ad/ArO)3/tacn)U([Eta]2-NNCPh2)]+ that underwent C--H activation, N-insertion, and H2 elimination to yield the uranium indazole complex [((Ad/ArO)3/tacn)U([Eta]2-3-phen(Ind))]. A comparatively bulkier diamantyl functionalized ligand system was developed and the reactivity of the corresponding U(III) precursor complex was investigated. The molecular structures obtained for [((Dia/ArO3/tacn)U(Cl)] and [((Dia/ArO3/tacn)U(NTMS)] revealed a much deeper coordination cavity than in those of corresponding uranium complexes supported by the tert-butyl and adamantyl ligand systems. The deeper hydrophobic pocket is potentially advantageous for activation and functionalization of alkanes. A highly reactive trivalent uranium complex was also prepared supported by a more flexible single N-anchored ligand, [((Ad/ArO)3/N)U]. This U(III) complex is reactive towards a wide range of substrates. For instance, reductive cleavage of CO2 was observed to form bridging carbonate complex [{((Ad/ArO)3/N)U}2/[Mu]-[Eta]1:[Kappa]2/-CO3)]. A rare transformation involving reductive coupling of CS2 was achieved generating uranium thiooxalate complex [{((Ad/ArO)3/N)U}2/[Mu-[Kappa]2:[Kappa]2-C2S4)]. Activation of organic azides such as azidotrimethylsilane yielded [((Ad/ArO)3/N)U(N3)] and [((Ad/ArO)3/N)U(NTMS)]. Uranium mesitylimide complex [((Ad/ArO)3/N)U(NMes)] can also be synthesized from activation of mesityl azide. The trivalent uranium complex [((Ad/ArO)3/N)U] can also activate chalcogenides such as elemental sulfur and selenium to form bridging chalcogenide complexes of the type [{((Ad/ArO)3/N)U}2/[Mu]-E)], E = S, Se. In the presence of Na/Hg, [Na2][{((Ad/ArO)3/N)U}2/[Mu]-E)2]-type complexes, E = S, Se, Te were also obtained.
Author : Anthony E. Vaughn
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (41 download)
Download or read book High Valent Uranium Dioxo and Imido Complexes written by Anthony E. Vaughn and published by . This book was released on 2008 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Early actinide elements have attracted considerable attention in recent years due to the need for rigorous advancements in spent nuclear fuel recycling and remediation technologies, and for their emerging versatility in organometallic chemistry. Whereas high oxidation state ions dominate environmental speciation, the corresponding high-valent organometallics are rare. These hexa- and pentavalent ions are often stabilized by the isoelectronic oxo or imido ligands, which result in robust molecular properties due to 5f/6d orbital involvement in multiple covalent bonding. The research discussed in this dissertation surveys the synthesis, isolation, and molecular and electronic structural characterization of uranyl(VI) and uranium(V)-imide complexes, and uncovers the influences imparted by a variety of functional ligand designs. In the opening report, salicylidene derived Schiff base chelates adapt to equatorial coordination and control uranyl(VI) photo- and electrochemical activity. In the second study, a ferrocenylcarboxylate ligand undergoes a transformation that renders an unprecedented bent uranyl(VI) moiety supported in a reversible coordination polymer. The final segment focuses on the rare uranium(V) oxidation state supported by pentamethylcyclopentadienyl and imido ancillary ligands in mono- and bimetallic complexes geared to elucidate the effects of ligand substitution and metal-metal communication on the 5f1 electronic configuration. Future directions and applications for each area are summarized.
Author : Patrick Bailey Hogsed
Publisher :
ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (135 download)
Download or read book Uranyl Complexes with Nitrogen and Sulfur Donor Bidentate Ligands: a Computational Modeling of Coordination Geometries, Thermodynamic Parameters, and Ligand Substituent Effects written by Patrick Bailey Hogsed and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Actinides represent a special group of metal ions that need to be extensively studied due to their presence in the environment with the construction of nuclear power plants, processing of minerals, and weapon production. Radioactive waste produced by nuclear fission contains several lanthanide and actinide metals, including uranium. The extraction of uranium from nuclear waste is an active area of research. To this end, numerous sulfur and nitrogen-donor ligands have been studied to assist with the nuclear extraction process. Computational chemistry investigations of actinide complexes will provide important insight into metal-ligand bonding and their thermodynamic properties in order to design effective actinide extracting agents. Current research work is focused on studying the coordination chemistry behavior and reaction energetics of a series of uranyl metal complexes with ethylenediamine, 1,2-ethanedithiol, and cysteamine ligands using density functional theory (DFT). Coordination preferences using nitrogen and sulfur-based chelation were evaluated in the gas phase. Nitrogen donor ethylenediamine ligand produced the lowest reaction Gibbs free energies, and sulfur donor cysteamine ligands had the highest values. Ligand substitution effects on uranyl metal-ligand bonding were studied using four substituent groups, CH3, CN, OCH3, and Cl. Electron donor CH3 and OCH3 groups provided relatively shorter metal-ligand bond distances and lower reaction Gibbs free energies. Electron withdrawing substituents resulted in longer metal-ligand bonding and higher reaction Gibbs free energies. Disubstitution of the chelating ligands amplifies the above effects. Future work will focus on exploring more substituents and solvent effects on uranyl metal-ligand complexation reaction using the above ligands.
Author :
Publisher :
ISBN 13 :
Total Pages : 1216 pages
Book Rating : 4.0/5 ( download)
Download or read book Nuclear Science Abstracts written by and published by . This book was released on 1976-06 with total page 1216 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Michael David Fabiano
Publisher :
ISBN 13 :
Total Pages : 54 pages
Book Rating : 4.:/5 (7 download)
Download or read book Basicity of Coordinating Ligands in Trivalent Uranium and Cerium Metallocene Complexes written by Michael David Fabiano and published by . This book was released on 1988 with total page 54 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Sergey Krivovichev
Publisher : Elsevier
ISBN 13 : 0080467911
Total Pages : 505 pages
Book Rating : 4.0/5 (84 download)
Download or read book Structural Chemistry of Inorganic Actinide Compounds written by Sergey Krivovichev and published by Elsevier. This book was released on 2006-12-08 with total page 505 pages. Available in PDF, EPUB and Kindle. Book excerpt: Structural Chemistry of Inorganic Actinide Compounds is a collection of 13 reviews on structural and coordination chemistry of actinide compounds. Within the last decade, these compounds have attracted considerable attention because of their importance for radioactive waste management, catalysis, ion-exchange and absorption applications, etc. Synthetic and natural actinide compounds are also of great environmental concern as they form as a result of alteration of spent nuclear fuel and radioactive waste under Earth surface conditions, during burn-up of nuclear fuel in reactors, represent oxidation products of uranium miles and mine tailings, etc. The actinide compounds are also of considerable interest to material scientists due to the unique electronic properties of actinides that give rise to interesting physical properties controlled by the structural architecture of respective compounds. The book provides both general overview and review of recent developments in the field, including such emergent topics as nanomaterials and nanoparticles and their relevance to the transfer of actinides under environmental conditions. * Covers over 2,000 actinide compounds including materials, minerals and coordination polymers* Summarizes recent achievements in the field* Some chapters reveal (secret) advances made by the Soviet Union during the 'Cold war'
Author : Ian M. Henderson
Publisher :
ISBN 13 :
Total Pages : 193 pages
Book Rating : 4.:/5 (815 download)
Download or read book Tuning the Properties of Metal-ligand Complexes to Modify the Properties of Supramolecular Materials written by Ian M. Henderson and published by . This book was released on 2012 with total page 193 pages. Available in PDF, EPUB and Kindle. Book excerpt: Supramolecular chemistry is the study of discreet molecules assembled into more complex structures though non-covalent interactions such as host-guest effects, pi-pi stacking, electrostatic effects, hydrogen bonding, and metal-ligand interactions. Using these interactions, complex hierarchical assembles can be created from relatively simple precursors. Of the supramolecular interactions listed above, metal-ligand interactions are of particular interest due to the wide possible properties which they present. Factors such as the denticity, polarizability, steric hindrance, ligand structure, and the metal used (among others) contribute to a dramatic range in the physical properties of the metal-ligand complexes. Particularly affected by these factors are the kinetic and thermodynamic properties of the complexes. As a result metal-ligand interactions can vary from inert to extremely transient. Of the vast number of ligands available for study, this dissertation will center on substituted terpyridine ligands, with a particular focus on terpyridine-functionalized polymers. While polymer-functionalized terpyridine ligands and their complexes with transition metals have been heavily studied, the physical properties, particularly the effects of polymer functionalization on the stability of bis complexes of terpyridines, remain unexplored. In the course of investigating the kinetic stability of these complexes, polymer functionalization techniques were developed which were found to increase the stability of the metal-ligand interactions compared to conventional techniques. In addition to studying the effect of terpyridine substituents, the effects of solvent on the stability of the complexes was studied as well. As polymer-bound terpyridine complexes are often studied in solvents other than water, knowledge of the stability of the complexes in organic solvents is important to create supramolecular structures with more precisely controlled properties. It was found that, for unsubstituted terpyridyl complexes, the stability of the complexes varied by as many as five orders of magnitude in common solvents. It is believed that this decrease in stability is the result of the ability of the solvent to facilitate the movement of the ligands from the first and second coordination spheres. Although a large part of this dissertation is dedicated to the study of the kinetic stability of terpyridine complexes, synthetic techniques involving terpyridine and its complexes were investigated as well. It was found that terpyridine functionalized polystyrene could be produced by direction functionalization of terpyridine with polystyryllithium. Additionally heterloleptic terpyridine-based iron complexes were produced with high purity by reduction of the mono terpyridine complex of iron(III) in the presence of a second, functionalized terpyridine ligand. The culmination of these studies was the synthesis of supramolecular organogels, which were crosslinked using metal-terpyridine complexes, yielding dynamic mechanical properties could be broadly tuned by varying the metal used to form the crosslinks.
Author : Charles E. Stuber
Publisher :
ISBN 13 :
Total Pages : 152 pages
Book Rating : 4.3/5 (91 download)
Download or read book Transplutonium Elements written by Charles E. Stuber and published by . This book was released on 1977 with total page 152 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Robert G. Riley
Publisher :
ISBN 13 :
Total Pages : 100 pages
Book Rating : 4.:/5 (7 download)
Download or read book Chemical Contaminants on DOE Lands and Selection of Contaminant Mixtures for Subsurface Science Research written by Robert G. Riley and published by . This book was released on 1992 with total page 100 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Philippe Kalck
Publisher : Springer Nature
ISBN 13 : 3031322509
Total Pages : 241 pages
Book Rating : 4.0/5 (313 download)
Download or read book Modes of Cooperative Effects in Dinuclear Complexes written by Philippe Kalck and published by Springer Nature. This book was released on 2023-05-23 with total page 241 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book presents recent advances in dinuclear complexes in which the metal-metal cooperative effect operates for obtaining substrate activation and high performance catalysts. Catalysis continues to be a fast expanding area to design efficient tools in synthesis and in industrial chemistry. It allows performing syntheses with short reaction times, atom economy, reduced consumption of energy and loss of reagents, and low level of wastes. Dinuclear complexes are known to be more efficient than the mononuclear analogues for the reaction rates and the selectivities. This book analyses the latest research, focusing on the key concepts, in building and using these dinuclear complexes. The book is aimed at researchers, graduate students and chemists at all levels in academia and industry.
Author : Benjamin Leon Dadds
Publisher :
ISBN 13 :
Total Pages : 158 pages
Book Rating : 4.:/5 (643 download)
Download or read book Coordination Chemistry Uranium and Lanthanide Complexes and Their Luminescence Properties written by Benjamin Leon Dadds and published by . This book was released on 2006 with total page 158 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author :
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ISBN 13 :
Total Pages : 988 pages
Book Rating : 4.:/5 (319 download)
Download or read book INIS Atomindex written by and published by . This book was released on 1988 with total page 988 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author : Kenneth D. Karlin
Publisher : John Wiley & Sons
ISBN 13 : 0471725552
Total Pages : 544 pages
Book Rating : 4.4/5 (717 download)
Download or read book Progress in Inorganic Chemistry written by Kenneth D. Karlin and published by John Wiley & Sons. This book was released on 2005-06-14 with total page 544 pages. Available in PDF, EPUB and Kindle. Book excerpt: The cutting edge of scientific reporting . . . PROGRESS in Inorganic Chemistry Nowhere is creative scientific talent busier than in the world ofinorganic chemistry experimentation. Progress in InorganicChemistry continues in its tradition of being the most respectedavenue for exchanging innovative research. This series providesinorganic chemists and materials scientists with a forum forcritical, authoritative evaluations of advances in every area ofthe discipline. With contributions from internationally renownedchemists, this latest volume offers an in-depth, far-rangingexamination of the changing face of the field, providing atantalizing glimpse of the emerging state of the science. "This series is distinguished not only by its scope and breadth,but also by the depth and quality of the reviews." -Journal of the American Chemical Society "[This series] has won a deservedly honored place on the bookshelfof the chemist attempting to keep afloat in the torrent of originalpapers on inorganic chemistry." -Chemistry in Britain CONTENTS OF VOLUME 54 * Atomlike Building Units of Adjustable Character: Solid-State andSolution Routes to Manipulating Hexanuclear Transition MetalChalcohalide Clusters (Eric J. Welch and Jeffrey R. Long) * Doped Semiconductor Nanocrystals: Synthesis, Characterization,Physical Properties, and Applications (J. Daniel Bryan and DanielR. Gamelin) * Stereochemical Aspects of Metal Xanthane Complexes: MolecularStructures and Supramolecular Self-Assembly (Edward R. T. Tiekinkand Ionel Haiduc) * Trivalent Uranium: A Versatile Species for Molecular Activation(Ilia Korobkov and Sandro Gambarotta) * Comparison of the Chemical Biology of NO and HNO: An InorganicPerspective (Katrina M. Miranda and David A. Wink) * Alterations of Nucleobase pKa Values upon Metal Coordination:Origins and Consequences (Bernhard Lippert) * Functionalization of Myoglobin (Yoshihito Watanabe and TakashiHayashi)
Author : Sarah Cook
Publisher :
ISBN 13 : 9781339125176
Total Pages : 191 pages
Book Rating : 4.1/5 (251 download)
Download or read book Principles of Molecular Design in the Development of Ligand Frameworks that Control the Primary and Secondary Coordination Spheres of Metal Ions written by Sarah Cook and published by . This book was released on 2015 with total page 191 pages. Available in PDF, EPUB and Kindle. Book excerpt: Metalloproteins have evolved to contain specific combinations of primary and secondary coordination spheres within their active sites that contribute to the high activity and selectivity of their chemical transformations. One approach to developing small molecule analogs with comparable reactivity is to design molecular constructs that exhibit similar control over aspects of the primary and secondary coordination spheres. This dissertation describes the design and reactivity of multifunctional ligands that position hydrogen-bond acceptors within the secondary coordination spheres of transition metal complexes. Two classes of ligands were studied: the first is a tetradentate, tripodal ligand ([MST]3−) that was previously demonstrated to support formation of heterobimetallic complexes containing a Mn center and a redox inactive metal ion. The extension to the Fe analog is described here, as well as the continued examination of the influence of group 2 metal ions on the properties and reactivity of both the Mn and Fe complexes. The most important finding of these studies is that Ca(II) and Sr(II) ions impart nearly identical influences on the Mn and Fe centers—a result with relevance to biological water oxidation. Reaction of [MnMST]- and [FeMST]- with oxygen-atom transfer reagents in the absence of secondary metal ions uncovered a limitation of the [MST]3− ligand system in which weak C–H bonds are susceptible to intramolecular oxidation. In order to address this limitation, ligand derivatives were designed that removed weak C–H bonds, which led to the observation of a putative Fe(IV)–oxo intermediate. The last two chapters of this dissertation describe the development of a new type of ligand that utilizes a tridentate, redox-active framework that has been shown to provide access to multi-electron transformations at first row transition metal centers. The first derivative of this ligand was shown to form dinuclear complexes of Fe, Co, and Cu with a pre-organized binding pocket for secondary metal ions. Modification of the steric bulk of the ligand prevented formation of these dinuclear complexes and instead supported mononuclear Fe and Co centers. The structural, electronic, and electrochemical properties of both of these series of complexes are described.
Author :
Publisher :
ISBN 13 :
Total Pages : 398 pages
Book Rating : 4.5/5 (38 download)
Download or read book Russian Chemical Reviews written by and published by . This book was released on 2000 with total page 398 pages. Available in PDF, EPUB and Kindle. Book excerpt:
