Download Free Synthesis And Reactivity Of Low Coordinate Cobalt Complexes And Ironi Alkyl Complexes Supported By Beta Diketiminate Ligand Book in PDF and EPUB Free Download. You can read online Synthesis And Reactivity Of Low Coordinate Cobalt Complexes And Ironi Alkyl Complexes Supported By Beta Diketiminate Ligand and write the review.

The use of FeCl 2 (THF) 1.5 lead to the synthesis of [PhTt tB u]FeCl that provided entry into new [PhTt tBu]FeX chemistry. [PhTt tBu]FeCl crystallizes as a five-coordinate chloride bridged dimer that is a high-spin ferrous complex with an S = 2 ground state. The metathetical reaction of [PhTt tBu]FeCl with the desired dialkylmagnesium reagent, R 2 Mg (R = Me, Et, Ph, Bn), in 1,4-dioxane/THF leads to the formation of high-spin, S = 2, electronically and coordinatively unsaturated four-coordinate organoiron(II) complexes of the type, [PhTt tBu]Fe(R) (R = Me, Et, Ph, Bn). Reaction of [PhTt tBu]Fe(R) (R = Me, Et, Ph) with CO yields the low-spin, S = 0, six-coordinate complexes [PhTt tBu]Fe(CO) 2 (R) (R = Me, Et, Ph). Carbonylation of [PhTt tBu]Fe(Bn) yields [PhTt tBu]Fe(CO) 2 (Bn) and the reduced monovalent species [PhTt tBu]Fe(CO) 2 . The reduction of [PhTt tBu]FeCl in the presence of a phosphine ligand, PMe 3 or PEt 3, yields the high-spin, S = 3/2, monovalent iron complexes, [PhTt tBu]Fe(PMe 3) or [PhTt tBu]Fe(PEt 3) in moderate yields. [PhTt tBu]Fe(PMe 3) reacts with CO producing the low-spin, S = 1/2, monovalent product [PhTt tBu]Fe(CO) 2 . X-ray crystallographic analysis confirms a five-coordinate, square pyramidal coordination geometry. [PhTt tBu]Fe(PMe 3) reacts with diphenylacetylene producing the high-spin, S = 3/2 product [PhTt tBu]Fe(PhC=CPh). X-ray crystallography confirms a five-coordinate, square pyramidal coordination geometry with PhC=CPh bound to the iron center in a symmetric, side-on eta 2 binding mode. [PhTt tBu]Fe(PMe 3) reacts with adamantyl azide producing the high-spin, S = 3/2 product, [kappa 2 -PhTt tBu]Fe(N 4 Ad 2). The dialkyltetraazadiene ligand exhibits nearly identical N-N bonds suggesting a delocalized ligand radical dialkyltetraazadiene resonance form. Efforts to model a catalytically inhibited form of COdH were performed by designing a simple Ni:Fe binuclear complex that provides the essential metal coordination spheres of the C-cluster active site. The scope of these studies was expanded to include a series of cyanide-bridged binuclear complexes, ('S 3 ')Ni-CN-M[Tp tBu] (M = Fe, Co, Ni, Zn). A similar coupling scheme was used to synthesize the copper(I) analogue, Et 4 N{('S 3 ')Ni-CN-Cu[Tp tBu]}. Two synthetic strategies were employed to investigate the formation of cyanide-bridged linkage isomers. The products of two different 13 CN labeled reactions intended to yield ('S 3 ')Ni-CN-Zn[Tp tBu] and ('S 3 ')Ni-NC-Zn[Tp tBu] were analyzed. Nearly identical infrared and 13 C NMR spectroscopic data provide additional evidence that ('S 3 ')Ni-CN-Zn[Tp tBu] is produced in both reactions.
This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.
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.
This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of σ-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first σ-SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into σ-bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of σ-SiSi, σ-CC and σ-CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of σ-CC and σ-CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.
Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn't require organic solvents), with special attention paid to 'greener' methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. - Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more - Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water - Includes experimental procedures, with examples of direct synthesis, at the end of each chapter
Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II: State-of-the-art and Perspectives provides a critical review of the state-of-the-art developments in industrially relevant processes connected to efficient and selective olefin upgrading. Specific attention is devoted to catalysts containing imine- and amine-based ligands. All the chapters in this book have been designed to provide a systematic account of the vast amount of information available for this type of catalyst as well as to highlight the factors that ultimately control the catalyst’s performance and productivity. A comprehensive panorama of catalyst precursors is presented, spanning from group 10 α-diimine complexes and iron and cobalt 2,6-bis(imino)pyridine derivatives, to vanadium, chromium, titanium, zirconium and lanthanide complexes supported by nitrogen-containing ligands. The authors of this collective work are currently involved in the development of imine-based catalysts for efficient and selective olefin upgrading and the majority of them have dedicated most of their scientific career to this important field. In writing this book, their major goal is to transfer as many ideas and experiences as possible to the global audience of scientists engaged in this area of research.
This book explores the development of the first open-shell heavier tetrylidyne complexes featuring a tetrel-centered unpaired electron, and unprecedented metallatetrylidynes containing a multiply-bonded, linear-coordinated single heavier tetrel atom embedded between two metal centers. The chemistry of compounds featuring triple bonds of the heavier Group-14 elements Si–Pb with transition metals is a very challenging research area, which combines modern molecular main-group element with transition-metal chemistry, and is of fundamental importance for the understanding of chemical bonding. During the last 15 years, the research in this area has witnessed considerable progress in isolating a series of closed-shell tetrylidyne complexes. However, despite numerous attempts, open-shell tetrylidyne complexes and heavier group 14 element congeners of metallacarbynes and carbide complexes remained inaccessible. In this book, readers will find more about the synthesis, full characterization and reactivity studies of these novel complexes that uncovered a plethora of exceptional products, including a novel m3-silicido complex, the first dimetallasilacumulene with a linear, two-coordinated single silicon atom and the first compounds of planar tetracoordinated silicon (ptSi) (Anti-van’t Hoff-Le Bell Silicon). Readers will also learn about the isolation and full characterization of the first room-temperature stable disilavinylidene, a silicon analogue of the very reactive vinylidenes (R2C=C:), and the first intermetallic plumbylidyne ligand transfer reactions.