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Design and Synthesis of Chiral Ligands and Their Applications in Transition
The Pennsylvania State University The Graduate School Department of Chemistry DESIGN AND SYNTHESIS OF CHIRAL LIGANDS AND THEIR APPLICATIONS IN TRANSITION METAL-CATALYZED ASYMMETRIC REACTIONS A Dissertation in Chemistry by Wei Li 2012 Wei Li Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2012 The dissertation of Wei Li was reviewed and approved* by the following: Gong Chen Assistant Professor of Chemistry Dissertation Advisor Chair of Committee Tom Mallouk Evan Pugh Professor of Material Chemistry and Physics Alex Radosevich Assistant Professor of Chemistry Qing Wang Associate Professor of Material Science and Engineering Xumu Zhang Professor of Chemistry Special Member Barbara J. Garrison Shapiro Professor of Chemistry Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Transition metal catalyzed reactions are among the most powerful and direct approaches for the synthesis of organic molecules. During the past several decades, phosphorous-containing ligands have been extensively studied in transition metal - catalyzed transformations particularly asymmetric hydrogenations. Development of new chiral ligands and efficient catalyst systems for various prochiral unsaturated substrates in asymmetric hydrogenations are the focus of this dissertation. An important family of atropisomeric biaryl bisphosphine ligands, C3*-TunePhos and related bisaminophosphines have been designed and synthesized. The Ru catalysts of the highly modular C3*-TunePhos have been proved to be highly efficient (up to 99.8% ee, up to 1,000,000 TON) for practical asymmetric hydrogenations of a wide range of unfunctionalized ketones as well as α-, β- keto esters and N-2-substituted allylphthalimides. The synthetic utility of bisaminophosphine ligands was studied for rhodium-catalyzed asymmetric hydrogenations of α-dehydroamino acid esters, affording up to 98% ee’s. -
Richardmooremscthesis1970 O
University of St Andrews Full metadata for this thesis is available in St Andrews Research Repository at: http://research-repository.st-andrews.ac.uk/ This thesis is protected by original copyright sOMd MBTAL 3ARB0NYL JOMPL^XBS OF THIOJARBUNYL JQKPUUNud BEING AM a.SC. THESIS PRESENTED TO THE UNIVERSITY OF ST. ANDREWS The thesis deals with three main subjects. Firstly, the preparation of a new class of organosulphur-metal carbonyl compounds is described. Secondly, an attempted preparation of sulphines is describee, and finally, a new method of preparing methylthioketones is described. The metal carbonyl complexes were prepared from three types of thiocarbonyl compound. Pyrao- and thiopyran-A—thiones were found to readily form complexes provided that the 3 and 5 positions on the nucleus were unsubstituted, or at the most, mono-substituted. Indolizine thioaldebydes were also found to form stable complexes with molybdenum hexacarbonyl, although in lower yields than with pyran- and thiopyranthiones. Also forming stable complexes, the pyrrolothiazole thioaldehydes. Some difficulty was experienced in assigning a molecular formula to these compondds as two possibilities remained after elementary analysis, namely the-rr-complex M(G0)3L and the er-complex M(G0)5L where M is the metal, and L is the ligand. The obvious solution to the problem, X-Ray crystallography, was ruled out by not being able to obtain large enough crystals of the complex. Similarly mass spectra was unhelpful in assigning a correct formula, as no recognised molecular ion peaks were discernible. However one peak to be recognised was MoCOS indicating that bonding is througn the thiocarbonyl sulphur, or in other words a <r—complex had been formed. -
Chemical Intercalation of Zerovalent Metals Into 2D Layered Bi2se3 Nanoribbons † † ‡ † † † § Kristie J
Article pubs.acs.org/JACS Chemical Intercalation of Zerovalent Metals into 2D Layered Bi2Se3 Nanoribbons † † ‡ † † † § Kristie J. Koski, Colin D. Wessells, Bryan W. Reed, Judy J. Cha, Desheng Kong, and Yi Cui*, , † Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States ‡ Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United States § SLAC National Accelerator Laboratory, Stanford Institute for Materials and Energy Sciences, 2575 Sand Hill Road, Menlo Park, California 94025, United States *S Supporting Information ABSTRACT: We have developed a chemical method to intercalate a variety of zerovalent metal atoms into two-dimen- sional (2D) layered Bi2Se3 chalcogenide nanoribbons. We use a chemical reaction, such as a disproportionation redox reaction, to generate dilute zerovalent metal atoms in a refluxing solution, which intercalate into the layered Bi2Se3 structure. The zerovalent nature of the intercalant allows superstoichiometric intercalation of metal atoms such as Ag, Au, Co, Cu, Fe, In, Ni, and Sn. We foresee the impact of this methodology in establishing novel fundamental physical behaviors and in possible energy applications. 1. INTRODUCTION Ni, and Sn. Some interesting effects that could arise with − 7−10 intercalation are superconductivity, such as in Cu Bi2Se3, Intercalation is the insertion of a guest species into a host 6 lattice. Intercalation into layered materials is essential to battery enhanced conductivity, or possibly opening a surface state gap electrodes, electrochromics, detergents, and solid lubricants and in topological insulator Bi2Se3. This method of zerovalent metal is important in exotic fundamental two-dimensional (2D) intercalation may also be extended to other layered materials. -
Synthesis, Characterization and Reactivity of Functionalized Iron-Sulfur Clusters As Bioinspired Hydrogenase Models
Technisch-Naturwissenschaftliche Fakultät Synthesis, Characterization and Reactivity of Functionalized Iron-Sulfur Clusters as Bioinspired Hydrogenase Models DISSERTATION zur Erlangung des akademischen Grades Doktor der Technischen Wissenschaften im Doktoratsstudium der Technischen Wissenschaften Eingereicht von: DI Manuel Kaiser Angefertigt am: Institut für Anorganische Chemie Beurteilung: Prof. Dr. Günther Knör Assoc.-Prof. Mario Waser Mitwirkung: Linz, November 2015 Eidesstattliche Erklärung Ich erkläre an Eides statt, dass ich die vorliegende Dissertation selbstständig und ohne fremde Hilfe verfasst, andere als die angegebenen Quellen und Hilfsmittel nicht benutzt bzw. die wörtlich oder sinngemäß entnommenen Stellen als solche kenntlich gemacht habe. Die vorliegende Dissertation ist mit dem elektronisch übermittelten Textdokument identisch. Linz, November 2015 ________________________________ Manuel Kaiser I Dipl.‐Ing. Manuel Kaiser Persönliche Daten Geburtsdatum 15.11.1985 Staatsangehörigkeit Österreich Familienstand ledig Telefon 0699/12123124 Mail [email protected] Adresse Johann‐Wilhelm‐Klein‐Straße 2‐4, 4040 Linz Ausbildung 10/2012 – 12/2015 Doktoratsstudium Technische Wissenschaften, JKU Linz Dissertation am Institut für Anorganische Chemie betreut von Prof. Dr. Günther Knör: „Synthesis, Characterization and Reactivity of Functionalized Iron‐Sulfur Clusters as Bioinspired Hydrogenase Models“ 10/2005 – 09/2012 Diplomstudium Technische Chemie, JKU Linz (Abschluss: Dipl.‐Ing.) Diplomarbeit am Institut für Anorganische Chemie -
Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc
Metal-Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc Richard H. Duncan Lyngdoh*,a, Henry F. Schaefer III*,b and R. Bruce King*,b a Department of Chemistry, North-Eastern Hill University, Shillong 793022, India B Centre for Computational Quantum Chemistry, University of Georgia, Athens GA 30602 ABSTRACT: This survey of metal-metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) n+ the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) , (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. -
Iron Pentacarbonyl
Poison Facts: Low Chemicals: Iron Pentacarbonyl Properties of the Chemical Iron carbonyl (pentacarbonyl iron), C5FeO5, is a yellow, oily liquid. It is pyrophoric in air and burns to Fe2O3 (Iron[III] oxide) and decomposes by light to Fe2(CO)9 and CO. It is practically insoluble in water, readily soluble in most organic solvents (ether, acetone, ethyl acetate) and slightly soluble in alcohol. The vapor is heavier than air and may travel along the ground. Distant ignition is possible, and it may explode on heating. It may also spontaneously ignite in contact with air. Iron pentacarbonyl is a strong reducing agent and reacts violently with oxidants. Uses of the Chemical Iron pentacarbonyl is prepared from iron (and iron compounds) and CO. It is used in the manufacture of powdered iron cores for high-frequency coils used in the radio and television industries. It is also used as an anti-knock agent in motor fuels and as a catalyst in organic reactions. Absorption, Distribution, Metabolism and Excretion (ADME) Iron pentacarbonyl can be absorbed into the body by inhalation of the vapor, through the skin or by ingestion. No other pharmacokinetic data is available. Clinical Effects of Acute Exposure • Ocular exposures: Iron pentacarbonyl is a local irritant and may cause irritation and injury to eyes. • Dermal exposures: The chemical may irritate the skin and mucous membranes. It may be absorbed through the skin. • Inhalation exposures: If inhaled, iron pentacarbonyl is a local irritant to the lungs and gastrointestinal tract. Symptoms of acute exposure to high concentrations resemble those of exposures to nickel carbonyl. -
Alkyl and Fluoroalkyl Manganese Pentacarbonyl Complexes As
En vue de l'obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par : Institut National Polytechnique de Toulouse (Toulouse INP) Discipline ou spécialité : Chimie Organométallique et de Coordination Présentée et soutenue par : M. ROBERTO MORALES CERRADA le jeudi 15 novembre 2018 Titre : Complexes de manganèse pentacarbonyle alkyle et fluoroalkyle comme modèles d'espèces dormantes de l'OMRP Ecole doctorale : Sciences de la Matière (SDM) Unité de recherche : Laboratoire de Chimie de Coordination (L.C.C.) Directeur(s) de Thèse : MME FLORENCE GAYET M. BRUNO AMEDURI Rapporteurs : M. GERARD JAOUEN, UNIVERSITE PARIS 6 Mme SOPHIE GUILLAUME, CNRS Membre(s) du jury : M. MATHIAS DESTARAC, UNIVERSITE TOULOUSE 3, Président M. BRUNO AMEDURI, CNRS, Membre M. HENRI CRAMAIL, INP BORDEAUX, Membre Mme FLORENCE GAYET, INP TOULOUSE, Membre A mi abuelo Antonio ‐ i ‐ ‐ ii ‐ Remerciements Ce travail a été réalisé dans deux unités de recherche du CNRS : le laboratoire de Chimie de Coordination (LCC) à Toulouse, au sein de l’équipe LAC2, et l’Institut Charles Gerhardt de Montpellier (ICGM), au sein de l’équipe IAM. Il a été codirigé par Dr. Florence Gayet et Dr. Bruno Améduri. Je tiens tout d’abord à remercier Dr. Azzedine Bousseksou, directeur du LCC, et Dr. Patrick Lacroix‐Desmazes, directeur de l’équipe IAM à l’ICGM, pour avoir accepté de m’accueillir au sein de ses laboratoires. Je remercie tout particulièrement mes directeurs de thèse, Dr. Florence Gayet et Dr. Bruno Améduri, pour m’avoir encadré durant ces trois années de doctorat. Un immense merci à tous les deux pour tous leurs conseils, leur patience et leurs connaissances qui m’ont apporté et qui m’ont permis de mener à bien ce travail. -
Some Reactions of Tris(Triphenylphosphine )-Dicarbonyliron( 0)
Indian Journal of Chemistry Vol. 21A, June 1982, pp. 579·582 Some Reactions of Tris(Triphenylphosphine )-dicarbonyliron( 0) S. VANCHEESAN Chemistry Department, Indian Institute of Technology, Madras 600 036 Received 20 October 1981; revised and accepted 15 February 1982 Tris(triphenylphospbine)-dicarbonyliron(O)(I) undergoes substitution reactions with trimethylphosphite, pyri- dine, dimethyl sulphoxide and methylisocyanide. Substitution takes place via dissociation of I to a 1 coordinativel1 unsaturated 16 electron complex, which is a highly reactive unstable intermediate. Both steric and electronic factors playa prominent role in deciding the feasibility of the reaction. Steric factor is expressed in terms of e, the cone angle of the ligand, and electronic factor in terms of Al mode of CO stretching frequency in Ni(CO)aL, where L is the ligand for which the electronic factor is expressed in terms of "CO. Ligands with cone angle e, greater than that of triphenyl- phosphine e.g. t-butylphosphine, do not react. In the reaction of I with molecular hydrogen and bromine, oxidative addition takes place. Diphenylacetylene forms two isomers, whereas carbon disulphide forms a n-complex on reaction with L MONG the d8 iron-phosphine complexes of (PPh3)2]+BF~ in absolute ethanol was allowed to the type fe(CO)6_" (PPh3) •• (where x = 1 to react overnight with triphenylphosphine in the A 3), the complexes with x = 1 and 2 had been presence of lithium metal. The resulting micro- studied to some extent>", Mono- and bis-phosphine crystalline solid was filtered and freed from phos- complexes can be prepared= by the reaction of phos- phine using hot ethanol and filtered. -
INFORMATION to USERS the Most Advanced Technology Has Been Used to Photo Graph and Reproduce This Manuscript from the Microfilm Master
INFORMATION TO USERS The most advanced technology has been used to photo graph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are re produced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. These are also available as one exposure on a standard 35mm slide or as a 17" x 23" black and white photographic print for an additional charge. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 0011152 Chemistry derived from the tetracarbonylates of group 8, [M(CO)4]2- (M = Fe, Ru, Os): Syntheses, characterization and derivative chemistry of the metalladiboranes, [M(CO )4 (j7 2-B 2 Hs)]~ (M = Ru, Os). -
Organo-Transition Metal Chemistry Some Studies
ORGANO-TRANSITION METAL CHEMISTRY SOME STUDIES IN ORGANO-TRANSITION METAL CHEMISTRY By COLIN CRINDROD, B.Sc. A Thesis Submitted to the Faculty of Graduate Studies in Partial Fulfilment of the Requirements for the Degree Master of Science McMaster University October 1966 MASTER OF SCIENCE (1966) MCMASTER UNIVERSITY (Chemistry) Hamilton, Ontario TITLE: Some Studies in Organo-Transition Metal Chemistry AUTHOR: Colin Grindrod, B.Sc. (Manchester University) SUPERVISOR: Dr. P. M. Maitlis NUMBER OF PAGES: iv, 71 SCOPE AND CONTENTS: The work described is an extension of the ligand-transfer reactions of substituted cyclobutadienes and cyclopentadienyls previously carried out by Maitlis et al. Efforts were directed particularly to ligand transfer reactions of n-allyl-transition metal complexes. The reactions of organic halides with metal carbonyls were also studied in attempts to isolate new organometallic derivatives. (ii) ACKNOWLEDGEMENTS The author wishes to express his sincere gratitude for the stimulating advice and constant encouragement provided by Dr. P. M. Maitlis, under whose guidance this work was carried out. Thanks are also extended to Imperial Oil Co. Ltd. for providing the financial support which made this study possible. (iii) CONTENTS Page INTRODUCTION Historical................................... 1 Cyclobutadiene-transition metal oompeeees... 7 Ligand-transfer reactions................... 10 Allyl-transition metal complexes............ 13 Reactions of metal carbonyls with organic halides.... ..................... 25 DISCUSSION -
Metal Carbonyls
MODULE 1: METAL CARBONYLS Key words: Carbon monoxide; transition metal complexes; ligand substitution reactions; mononuclear carbonyls; dinuclear carbonyls; polynuclear carbonyls; catalytic activity; Monsanto process; Collman’s reagent; effective atomic number; 18-electron rule V. D. Bhatt / Selected topics in coordination chemistry / 2 MODULE 1: METAL CARBONYLS LECTURE #1 1. INTRODUCTION: Justus von Liebig attempted initial experiments on reaction of carbon monoxide with metals in 1834. However, it was demonstrated later that the compound he claimed to be potassium carbonyl was not a metal carbonyl at all. After the synthesis of [PtCl2(CO)2] and [PtCl2(CO)]2 reported by Schutzenberger (1868) followed by [Ni(CO)4] reported by Mond et al (1890), Hieber prepared numerous compounds containing metal and carbon monoxide. Compounds having at least one bond between carbon and metal are known as organometallic compounds. Metal carbonyls are the transition metal complexes of carbon monoxide containing metal-carbon bond. Lone pair of electrons are available on both carbon and oxygen atoms of carbon monoxide ligand. However, as the carbon atoms donate electrons to the metal, these complexes are named as carbonyls. A variety of such complexes such as mono nuclear, poly nuclear, homoleptic and mixed ligand are known. These compounds are widely studied due to industrial importance, catalytic properties and structural interest. V. D. Bhatt / Selected topics in coordination chemistry / 3 Carbon monoxide is one of the most important π- acceptor ligand. Because of its π- acidity, carbon monoxide can stabilize zero formal oxidation state of metals in carbonyl complexes. 2. SYNTHESIS OF METAL CARBONYLS Following are some of the general methods of preparation of metal carbonyls. -
Guide for the Selection of Personal Protective Equipment for Emergency First Responders
U.S. Department of Justice Office of Justice Programs National Institute of Justice National Institute of Justice Law Enforcement and Corrections Standards and Testing Program Guide for the Selection of Personal Protective Equipment for Emergency First Responders NIJ Guide 102–00 Volume I November 2002 U.S. Department of Justice Office of Justice Programs 810 Seventh Street N.W. Washington, DC 20531 John Ashcroft Attorney General Deborah J. Daniels Assistant Attorney General Sarah V. Hart Director, National Institute of Justice For grant and funding information, contact: Department of Justice Response Center 800–421–6770 Office of Justice Programs National Institute of Justice World Wide Web Site World Wide Web Site http://www.ojp.usdoj.gov http://www.ojp.usdoj.gov/nij U.S. Department of Justice Office of Justice Programs National Institute of Justice Guide for the Selection of Personal Protective Equipment for Emergency First Responders NIJ Guide 102-00, Volume I Dr. Alim A. Fatah1 John A. Barrett2 Richard D. Arcilesi, Jr.2 Charlotte H. Lattin2 Charles G. Janney2 Edward A. Blackman2 Coordination by: Office of Law Enforcement Standards National Institute of Standards and Technology Gaithersburg, MD 20899–8102 Prepared for: National Institute of Justice Office of Science and Technology Washington, DC 20531 November 2002 This document was prepared under CBIAC contract number SPO-900-94-D-0002 and Interagency Agreement M92361 between NIST and the Department of Defense Technical Information Center (DTIC). NCJ 191518 1National Institute of Standards and Technology, Office of Law Enforcement Standards. 2Battelle Memorial Institute. National Institute of Justice Sarah V. Hart Director This guide was prepared for the National Institute of Justice, U.S.