The objective of this research project is to determine the special features of complexes of yttrium and the lanthanide metals which will allow the design and synthesis of materials with unique chemical, physical, and catalytic properties. Past studies of yttrium and lanthanide metal alkyl and hydride complexes stabilized by cyclopentadienyl co-ligands have shown that a substantial, often singular, organometallic chemistry is available via these metals. More extensive utilization of the chemical opportunities available through yttrium and the lanthanides would be possible, however, if stabilizing ancillary ligand systems less sensitive to oxidation and protonolysis than cyclopentadienides could be developed. Alkoxide ligands are attractive in this regard and our recent research had focused on alkoxides and the special opportunities they can provide to these metals. 6 refs., 10 figs.

The objective of this research project is to determine the special features of complexes of yttrium and the lanthanide metals which will allow the design and synthesis of materials with unique chemical, physical, and catalytic properties. Past studies of yttrium and lanthanide metal alkyl and hydride complexes stabilized by cyclopentadienyl co-ligands have shown that a substantial, often singular, organometallic chemistry is available via these metals. More extensive utilization of the chemical opportunities available through yttrium and the lanthanides would be possible, however, if stabilizing ancillary ligand systems less sensitive to oxidation and protonolysis than cyclopentadienides could be developed. Alkoxide ligands are attractive in this regard and our recent research had focused on alkoxides and the special opportunities they can provide to these metals. 6 refs., 10 figs.

The Lanthanides and Actinides: Synthesis, Reactivity, Properties and Applications constitutes an introduction to and comprehensive coverage of f-block chemistry encompassing the following areas: periodicity, natural occurrence and extraction, separations, electronic structure, coordination chemistry, organometallic chemistry, small molecule activation, catalysis, organic synthesis applications, magnetism, spectroscopy, computation, materials, photonics, solar cell technology, biological imaging, and technological applications. Under these subject areas the book provides a broad but deep coverage, providing basic overviews as well as detailed chapters on specific areas.This book, targeted at academics, postgraduates and advanced undergraduates, will serve as an ideal introductory text and key reference work to the Lanthanides and Actinides.

This dissertation focuses on the synthesis, characterization, and reactivity of unique organometallic complexes of yttrium, the lanthanides, and uranium in efforts to expand the limits of known redox chemistry of these elements. The results in this dissertation arose from investigations of previously established reduction reactions involving these metal ions that were not fully understood. In general, rare metal and actinide complexes of formula A3M and A22A'M (A = substituted cyclopentadienyl; A' = different monoanionic ligand; M = yttrium, lanthanide, uranium) were reacted with a variety of bases, alkyllithium reagents, azides, and alkali metals under different conditions. These investigations led to several new examples of substrate reduction and small molecule activation, and in some cases, gave insight into how these complicated reduction processes might be occurring. In the course of these studies, eight new oxidation states were discovered: the first examples of molecular complexes of the following ions, Y2, Ho2, Er2+, Tb2+, Pr2+, Gd2+, Lu2+, and U2+.

This dissertation develops f element chemistry by investigating and comparing the synthesis, coordination chemistry, and reactivity of lanthanide and actinide metal complexes with diazoalkane derivatives and guanidinates. The bis(cyclopentadienyl) ligand unit, [(n5-C5ME5)2]2-, was used to conduct these studies since it has previously proven to be a reliable route for investigating new ligands in f element chemistry. This is because it is relatively inert, provides solubility and stability to the reactive metal center, and allows spectroscopic and structural data to be obtained that is useful for analyzing this chemistry. Diazoalkanes, RRLCN2, are of interest because they are important organic substrates that are useful as carbene precursors and as reagents for the synthesis of heterocyclic compounds. Although the chemistry of diazoalkanes with the transition metals has been heavily studied, little is known about f element chemistry with these compounds. The lanthanides and actinides are different in their behavior with diazoalkanes. Lanthanides make cyanoamide complexes that can be converted by their reaction with nitriles to complexes of 1,2,3-triazoles, which are heterocycles with pharmaceutical, industrial, and agrochemical applications. In contrast, uranium makes very soluble products that do not react with nitriles. A facile synthetic route to hydrazonato complexes was also developed from lanthanide allyl complexes and diazoalkanes during this study. The chemistry of the bicyclic guanidinate ligand, (hpp)1-, was examined with the f elements because this ligand has the potential to stabilize higher oxidation states which are rare with the f elements. The (hpp)1- ligand can be readily incorporated into complexes of Ln3+, U3+, and U4+ and it can stabilize rare examples of mono-alkyl, hydride, and "tuck-in", (n5:n1-C5Me4CH2)2- U4+ complexes as well as U5+ in some cases. The reactivity of the uranium "tuck-in" complex was examined because this unit is frequently proposed as an intermediate in mechanistic schemes involving alkyl C-H bond activation with the f elements. The effect of the {(C5Me5)2(hpp)}3- ligand combination on uranium mono-alkyl and hydride reactivity was also examined. Altogether, the results from these studies expand our knowledge of f element chemistry and highlight the differences in chemical reactivity of the f elements compared to the transition metals.

. Covers the literature in depth from 1982-1994, thus building on the original nine volumes . 14 volume set . 8750 pages approx . Volumes 1-9 provide a detailed account of the organic chemistry of both main group and transition elements . Volume 10 deals with compounds containing heteronuclear metal-metal bonds . Volume 11 describes the use of main group organometallic compounds in organic synthesis . Volume 12 is devoted to the use of transition metal orgnometallic compounds in organic synthesis . Volume 13 consists of a comprehensive index of all organometallic structures studied by diffraction methods . Volume 14 contains subject and formula indexes covering Volumes 1-12

The only introduction into the exciting chemistry of Lanthanides and Actinides. The book is based on a number of courses on "f elements" The author has a long experience in teaching this field of chemistry Lanthanides have become very common elements in research and technology applications; this book offers the basic knowledge The book offers insights into a vast range of applications, from lasers to synthesis The Inorganic Chemistry: A Textbook series reflects the pivotal role of modern inorganic and physical chemistry in a whole range of emerging areas, such as materials chemistry, green chemistry and bioinorganic chemistry, as well as providing a solid grounding in established areas such as solid state chemistry, coordination chemistry, main group chemistry and physical inorganic chemistry. Lanthanide and Actinide Chemistry is a one-volume account of the Lanthanides (including scandium and yttrium), the Actinides and the Transactinide elements, intended as an introductory treatment for undergraduate and postgraduate students. The principal features of these elements are set out in detail, enabling clear comparison and contrast with the Transition Elements and Main Group metals. The book covers the extraction of the elements from their ores and their purification, as well as the synthesis of the man-made elements; the properties of the elements and principal binary compounds; detailed accounts of their coordination chemistry and organometallic chemistry, from both preparative and structural viewpoints, with a clear explanation of the factors responsible for the adoption of particular coordination numbers; spectroscopy and magnetism, especially for the lanthanides, with case studies and accounts of applications in areas like magnetic resonance imaging, lasers and luminescence; nuclear separations and problems in waste disposal for the radioactive elements, particularly in the context of plutonium. Latest developments are covered in areas like the synthesis of the latest man-made elements, whilst there is a whole chapter on the application of lanthanide compounds in synthetic organic chemistry. End-of-chapter questions suitable for tutorial discussions are provided, whilst there is a very comprehensive bibliography providing ready access to further reading on all topics.

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.

Organometallic Syntheses, Volume 3 focuses on the synthesis of compounds containing carbon-metal bonds, including ligands, compounds, chlorides, and derivatives. The selection first elaborates on bis(cyclopentadienyl) organolanthanide and organoyttrium chloride, methyl, and hydride complexes and base stabilized alkali metal halide adducts of bis (pentamethylcyclopentadienyl) lanthanide chlorides. The text then examines cyclopentadienyl metal carbonyl and nitrosyl derivatives, ferrocenylamine, cobalticinium and rhodicinium salts, and alkyl transition metal derivatives. The publication takes a look at transition metal complexes containing organophosphorus ligands, transition metal derivatives containing chalcogen ligands, and coinage metal derivatives. The text also reviews transition metal organometallic compounds, including compounds of group IA, IIA, IIB, and IVA. The selection is a vital reference for researchers interested in the synthesis of compounds containing carbon-metal bonds.