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| Author | : Patrick R. M. Talbot (Graduate student) |
| Publisher | : |
| Total Pages | : 0 |
| Release | : 2019 |
| Genre | : Ligands |
| ISBN | : |
| Author | : Wenliang Huang |
| Publisher | : |
| Total Pages | : 167 |
| Release | : 2013 |
| Genre | : |
| ISBN | : |
Rare-earths are a group of metals with fascinating physical properties and intriguing chemical reactivity. Organometallic rare-earth chemistry is of particular interest because of the increasing number of their applications in industry and consumer goods as well as the importance of understanding their physical and chemical properties. Despite the dominance of the trivalent oxidation state, recently, low-valent organometallic rare-earth compounds were characterized and showed interesting reactivity toward various molecules. The theme of this thesis is the reduction chemistry of rare-earth metal complexes. By utilizing an electronically and geometrically flexible ferrocene diamide ligand (NN^TBS = fc(NSi^tBuMe2)2, fc =1,1'-ferrocenediyl), unprecedented reactivity was discovered together with the synthesis and characterization of a series of rare-earth metal arene complexes. The fruitful reduction chemistry allowed: (1) the discovery of a new aromatic C-H and C-F bond activation mechanism for rare-earths; (2) the synthesis of the first scandium naphthalene complex and a reactivity study on P4 activation by rare-earth arene complexes; (3) the isolation and characterization of a 6C, 10[pi]-electron aromatic system stabilized by coordination to rare-earth metal ions. Recently, an improved method to access paramagnetic rare-earth starting materials for organometallic chemistry was developed in order to study the physical and chemical properties of paramagnetic rare-earth biphenyl complexes.
| Author | : Markus Niederberger |
| Publisher | : Springer Science & Business Media |
| Total Pages | : 223 |
| Release | : 2009-09-17 |
| Genre | : Science |
| ISBN | : 1848826710 |
Metal Oxide Nanoparticles in Organic Solvents discusses recent advances in the chemistry involved for the controlled synthesis and assembly of metal oxide nanoparticles, the characterizations required by such nanoobjects, and their size and shape depending properties. In the last few years, a valuable alternative to the well-known aqueous sol-gel processes was developed in the form of nonaqueous solution routes. Metal Oxide Nanoparticles in Organic Solvents reviews and compares surfactant- and solvent-controlled routes, as well as providing an overview of techniques for the characterization of metal oxide nanoparticles, crystallization pathways, the physical properties of metal oxide nanoparticles, their applications in diverse fields of technology, and their assembly into larger nano- and mesostructures. Researchers and postgraduates in the fields of nanomaterials and sol-gel chemistry will appreciate this book’s informative approach to chemical formation mechanisms in relation to metal oxides.
| Author | : Christopher Matthew Kotyk |
| Publisher | : |
| Total Pages | : 132 |
| Release | : 2015 |
| Genre | : |
| ISBN | : 9781321996111 |
This dissertation describes the synthesis, characterization, and reactivity of organometallic complexes of yttrium and the lanthanides in an effort to more completely understand the nature of a recently-discovered class of +2 ions of these rare earth metals. The reactivity of complexes of a new set of Ln2+ ions (Ln = rare earth metal) with unprecedented 4fn5d1 electron configurations has been explored to expand the unique chemistry possible with the rare earth elements. The isolation of unexpected reaction products is described as well as the discovery of a new divalent lanthanide system and the utilization of solvent-free mechanochemical synthesis for established rare earth organometallic species. In Chapter 1, the reactivity of the highly-reducing, air-, moisture-, and temperature-sensitive divalent lanthanide complexes [K(2.2.2-cryptand)][Cp'3Ln] (Ln = Y, La, Ce, Dy) is characterized by examining reactions with aromatic organic substrates of known reduction potential. Complexes of the 4fn5d1 Ln2+ ions reduce naphthalene and biphenyl within minutes to form a new class of reduced aromatic complexes, [K(2.2.2-cryptand)][Cp'2Ln(n4-C10H8)] (Ln = Y, La, Ce, Dy) and [K(2.2.2-cryptand)][Cp'2Y(n6-C6H5Ph)], respectively. The naphthalene reactions also produced the previously unobserved ligand redistribution products [K(2.2.2-cryptand)][Cp'4Ln] (Ln = Y, La), which show the effect of the lanthanide contraction on structure as the lanthanum complex has four n5-Cp' rings while yttrium has three n5-Cp' rings and one n1-Cp' ring.
| Author | : Timothy Tan Thatt Yang |
| Publisher | : CRC Press |
| Total Pages | : 258 |
| Release | : 2012-06-20 |
| Genre | : Science |
| ISBN | : 9814364207 |
This book provides in-depth aspects of nanotechnology of rare earth (RE) materials. It starts with a review on the physical and chemical properties of RE elements, followed by a discussion on various strategies in fabricating nanosized RE materials. It describes various techniques in derivatizing surface molecules onto nanosized RE materials. A con
| Author | : Ashley Sara Harvey |
| Publisher | : |
| Total Pages | : 252 |
| Release | : 2005 |
| Genre | : |
| ISBN | : |
| Author | : Mikhail Bochkarev |
| Publisher | : Springer |
| Total Pages | : 533 |
| Release | : 2012-12-24 |
| Genre | : Science |
| ISBN | : 9789401041614 |
The present book is based on the work of M.N.Bochkarev, G.S.Kalinina, L.N. zakharov and S.Ya.Khorshev. The Russian edition of that book appeared under the same title in 1989 and covered literature data up to the middle of 1986. Since that time the number of publications on this subject increased significantly. In this volume we include all the data published up to the end of 1990, as well as some of the most important relevant articles of 1991. Therefore, this book should be considered as a new book, devoted to the same problems, rather than as just a translation of the mentioned issue. This book deals with compounds of scandium, yttrium, lanthanum and lanthanoids containing direct metal-carbon bond, Le. with the real organometallic complexes of these metals. Besides, the volume includes the rare earth complexes, in which organic ligand is bonded to the metal atom via the atom of another element of the Periodic Table. In other words, the book includes all classes of rare earth organoderivatives. Carboxilates, fl-diketonates and related chelates are the exceptions, because their properties are closer to inorganic compounds and they were fully described elsewhere. It should be noted, that "rare earth elements", "rare earth metals", "lanthanoids" and related terms are used in this book for indicating scandium, yttrium, lanthanum and the following 14 elements of the Periodic Table.
| Author | : G. Adachi |
| Publisher | : Springer Science & Business Media |
| Total Pages | : 263 |
| Release | : 2006-07-10 |
| Genre | : Science |
| ISBN | : 1402025696 |
Binary Rare Earth Oxides is the first book in the field of rare earth oxides that provides coverage from the basic science through to recent advances. This book introduces the unique characteristics of the binary rare earth oxides with their chemistry, physics and applications. It provides a comprehensive review of all the characteristics of rare earth oxides, essential for scientists and engineers involved with rare earths, oxides, inorganic materials, ceramics, and structures. The binary rare earth oxides bring us a variety of interesting characteristics. Understanding their fundamental mechanisms builds a bridge between solid-state chemistry and materials science. The book begins with a brief introduction to binary rare earth oxides, their physical and chemical stabilities, polymorphism, crystal structures and phase transformation and the association with current applications. The book goes on to present the band structure of the oxides using several quantum chemical calculations, which belong to a newly developed area in the binary rare earth oxides. Central to this chapter are the characterizations of electrical, magnetic and optical properties, as well as details of single crystal growth and particle preparation methods that have progressed in recent years. Later chapters concentrate on thermo-chemical properties and trace determination techniques. The final chapter contains a variety of useful applications in various fields such as phosphors, glass abrasives, automotive catalysts, fuel cells, solid electrolytes, sunscreens, iron steels, and biological materials. This book is an invaluable resource for materials scientists and solid-state physicists and chemists with an interest in rare earth oxides, as well as advanced students and graduates who require an approach to familiarize them with this field. This book provides guidance through a comprehensive review of all the characteristics of binary rare earth oxides.
| Author | : Jonathan Lee Brosmer |
| Publisher | : |
| Total Pages | : 155 |
| Release | : 2017 |
| Genre | : |
| ISBN | : |
Reliable transformation of low-cost rare-earth metal oxides to organometallic rare-earth metal complexes is a prerequisite for the advancement of non-aqueous rare-earth metal chemistry. We have recently developed an in situ method to prepare rare-earth alkyl and halide precursors supported by a diamidoferrocene NNfc, 1,1'-fc(NSiMe2Bu)2, as an ancillary ligand. We extended the scope of this method to other lanthanide ions including those that are redox active, such as cerium, praseodymium, samarium, terbium, thulium, and ytterbium. Specifically, samarium trisbenzyl could be generated in situ and then converted to the corresponding samarium benzyl or iodide complexes in good yield. However, it was found that ytterbium trisbenzyl could not be formed cleanly and the consequent conversion to ytterbium iodide complex was low yielding. By adapting an alternative route, the desired ytterbium chloride precursor could be obtained in good yield and purity. The synthesis and characterization of two yttrium alkyl complexes supported by a bisphosphinimine ferrocene ligand, NPfc (1,1 -di(2,4-di-tert-butyl-6-diphenylphosphiniminophenoxy)ferrocene), were accomplished. Although (NPfc)Y(CH2Ph) and (NPfc)Y(CH2SiMe3) could be structurally characterized, these compounds are thermally sensitive and decompose at ambient temperature within hours. Their characterization was accomplished by NMR spectroscopy, electrochemical measurements, and elemental analysis. Reactivity studies were also carried out; however, the lack of prolonged thermal stability at ambient temperature of these molecules led to decomposition before a clean transformation to reaction products could be observed. The synthesis and characterization of Ln-C4Ph4-K, [(NNTBS)Ln( 2-C4Ph4)][K(THF)x] (Ln = Sc, Y, Lu), rare-earth metal complexes supported by a ferrocene diamide ligand, NNTBS (NNTBS = fc(NSitBuMe2)2, fc = 1,1 -ferrocenediyl), were accomplished. The preparation of the half-sandwich compounds, Ln-naph-K, [(NNTBS)Ln( -C10H8)][K(THF)2] (Ln = Sc, Y, Lu, La), was necessary in order to obtain high yields of rare-earth metallacyclopentadienes. Unlike Y and Lu, La did not show the same reactivity toward PhCCPh. The characterization of the new metal complexes was accomplished by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.
| Author | : Samuel C. Levy |
| Publisher | : |
| Total Pages | : 80 |
| Release | : 1962 |
| Genre | : Acetates |
| ISBN | : |
