In Presenting the Dissertation As a Partial Fulfillment of The
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Reducing Mg Anode Overpotential Via Ion Conductive Surface Layer Formation by Iodine Additive
COMMUNICATION Electrolytes www.advenergymat.de Reducing Mg Anode Overpotential via Ion Conductive Surface Layer Formation by Iodine Additive Xiaogang Li, Tao Gao, Fudong Han, Zhaohui Ma, Xiulin Fan, Singyuk Hou, Nico Eidson, Weishan Li,* and Chunsheng Wang* Another challenge is the development Electrolytes that are able to reversibly deposit/strip Mg are crucial for of electrolytes that can effectively utilize rechargeable Mg batteries. The most studied complex electrolytes based an Mg metal anode. Extensive effort has on Lewis acid-base chemistry are expensive, difficult to be synthesized, and been put in to develop electrolytes capable of reversibly depositing/stripping Mg. show limited anodic stability. Conventional electrolytes using simple salts Most work has focused on complex elec- such as Mg(TFSI)2 can be readily synthesized, but Mg deposition/stripping in trolytes that allow fast and reversible Mg these simple salt electrolytes is accompanied by a large overpotential due to deposition/stripping. Such electrolytes the formation of a surface layer on the Mg metal with a low Mg ion conduc- were first proposed by Aurbach’s group [8] tivity. Here the overpotential for Mg deposition/stripping in a simple salt, in 2000, and subsequently they devel- oped the all phenyl complex showing high Mg(TFSI) -1,2-dimethoxyethane (DME), electrolyte is significantly reduced by 2 anodic stability.[9] Later, a non-nucleophilic −3 adding a small concentration of iodine (≤50 × 10 M) as an additive. Mecha- electrolyte, Mg-HMDS, was developed by nism studies demonstrate that an Mg ion conductive solid MgI2 layer is Muldoon and co-workers, and Fichtner formed on the surface of the Mg metal and acts as a solid electrolyte inter- and co-workers for Mg/S batteries.[10,11] To eliminate the organic Grignard species in face. -
WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08F 210/16 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/US20 15/03 1952 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 2 1 May 2015 (21 .05.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 14/284,689 22 May 2014 (22.05.2014) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: CHEVRON PHILLIPS CHEMICAL COM¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, PANY LP [US/US]; 10001 Six Pines Drive, The Wood TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, lands, TX 77380 (US). -
Addition of a Grignard Reagent to an Ester: Formation of a Tertiary Alcohol
Addition of a Grignard Reagent to an Ester: Formation of a Tertiary Alcohol Introduction: Grignard reagents are important and versatile reagents in organic chemistry. In this experiment, you will prepare a Grignard reagent and react it with an ester to prepare a tertiary alcohol. Specifically, in this reaction you will prepare phenyl magnesium bromide from bromobenzene and magnesium metal and then react it with methyl benzoate to prepare triphenylmethanol (Figure 1). In this reaction, two equivalents of phenylmagnesium bromide add to methyl benzoate. Note: Grignard reagents are sensitive to water. ALL glassware must be completely clean and dry. Reagents have been stored over molecular sieves to keep them dry in storage, but you should also keep containers closed as much as possible. Finally, water in the air can also react with the Grignard reagents over time. To successfully prepare triphenylmethanol in this experiment, you will need to be well organized and not take too much time between steps. Figure 1. O 1) Me O OH Br Mg MgBr THF + 2) H3O triphenylmethanol Mechanism: The formation of Grignard reagents from aryl halides is a complex mechanism, which takes place on the surface of the magnesium metal. You do not need to concern yourself with the details of this step of the mechanism. Figure 2. MgBr O Bu MgBr Bu MgBr O + OH O Bu MgBr O H3O Me OEt Bu Me OEt Me Bu Me Bu Me –EtOMgBr Bu Bu The mechanism of the reaction of a Grignard reagent with an ester is shown in Figure 2 (using methyl propionate and butylmagnesium bromide). -
Net Ionic Equation Worksheet Answers
Honors Chemistry Name__________________________________ Period_____ Net Ionic Equation Worksheet READ THIS: When two solutions of ionic compounds are mixed, a solid may form. This type of reaction is called a precipitation reaction, and the solid produced in the reaction is known as the precipitate. You can predict whether a precipitate will form using a list of solubility rules such as those found in the table below. When a combination of ions is described as insoluble, a precipitate forms. There are three types of equations that are commonly written to describe a precipitation reaction. The molecular equation shows each of the substances in the reaction as compounds with physical states written next to the chemical formulas. The complete ionic equation shows each of the aqueous compounds as separate ions. Insoluble substances are not separated and these have the symbol (s) written next to them. Water is also not separated and it has a (l) written next to it. Notice that there are ions that are present on both sides of the reaction arrow –> that is, they do not react. These ions are known as spectator ions and they are eliminated from complete ionic equation by crossing them out. The remaining equation is known as the net ionic equation. For example: The reaction of potassium chloride and lead II nitrate Molecular Equation: 2KCl (aq) + Pb(NO3)2 (aq) -> 2KNO3 (aq) + PbCl2 (s) + - 2+ 3– + – Complete Ionic Equation: 2K (aq) + 2Cl (aq) + Pb (aq) + 2NO (aq) -> 2K (aq) + 2NO3 (aq) + PbCl2 (s) - 2+ Net Ionic Equation: 2Cl (aq) + Pb (aq) -> PbCl2 (s) Directions: Write balanced molecular, ionic, and net ionic equations for each of the following reactions. -
Copper(I) Complexes of P‐Stereogenic Josiphos and Related Ligands
Full Papers doi.org/10.1002/ejoc.202100146 Copper(I) Complexes of P-Stereogenic Josiphos and Related Ligands Ross A. Arthurs,[a] Alice C. Dean,[a] David L. Hughes,[a] and Christopher J. Richards*[a] Starting from (R)-Ugi’s amine, diastereoselective lithiation avoiding the isolation of air-sensitive phosphine intermediates. followed by Ar’PCl2 and then Ar’’MgBr led to the generation, as This protection methodology was also applied to the synthesis single diastereoisomers, of (R,Sp,Sphos) [Ar’=Ph, Ar’’=o-Tol] and of Josiphos/CuCl complexes derived from PCl3. In addition, (R,Sp,Rphos) [Ar’=o-Tol, Ar’’= Ph] PPFA ligand derivatives. Amine related bulky cobalt-sandwich complex-based derivatives were substitution of both with HPCy2 gave P-stereogenic Josiphos also obtained. Preliminary investigation revealed isolated CuCl ligands, and then addition of CuCl, the corresponding copper(I) complexes as competent catalyst precursors for enantioselec- complexes. The latter were also generated by using borane P tive conjugate addition reactions. and N protecting groups and in situ Cu(I) complexation, Introduction Although many ligands have been developed for application in asymmetric synthesis, relatively few have found widespread use. Of these so-called ‘privileged’ ligands,[1] one of the most successful class are the ferrocene-based Josiphos ligands A.[2] Numerous derivatives are known, obtained by varying the identity of R’ and R’’, and many are commercially available. This has aided the incorporation of A into many ligand screening exercises, often leading to a successful outcome.[3] In particular, in situ generated Josiphos-copper complexes have been applied Scheme 1. -
The Ozonolysis of Phenyl Grignard Reagent
University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 1971 The ozonolysis of phenyl Grignard reagent Gale Manning Sherrodd The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Sherrodd, Gale Manning, "The ozonolysis of phenyl Grignard reagent" (1971). Graduate Student Theses, Dissertations, & Professional Papers. 8297. https://scholarworks.umt.edu/etd/8297 This Thesis is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. THE OZONOLYSIS OF PHENYL GRIGNARD REAGENT By Gale M. Sherrodd B.S., Rocky Mountain College, I969 Presented in partial fulfillment of the requirements for the degree of Master of Arts for Teachers UNIVERSITY OF MONTANA 1971 Approved by: Chairman, Board of Examiners De^ , Graduate *School / n ? / Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: EP39098 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMT DiMMtstion PuWiahing UMI EP39098 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author. -
CF 7.4 V2.Indd
2007 VOLUME 7 NUMBER 4 Product Directory Grignard and Organozinc Reagents RIEKE® HIGHLY REACTIVE METALS GRIGNARD REAGENTS ORGANOZINC HALIDES DIALKYLMAGNESIUM AND DIALKYZINC REAGENTS 2-Pyridylzinc bromide: a shelf-stable 2-pyridyl anion equivalent; an important motif in many pharmacologically active molecules. sigma-aldrich.com 2 Table of Contents Sigma-Aldrich is committed to providing the most extensive portfolio of high-quality Grignard, organozinc, and other organometallic reagents, and we continually expand our product listing. Within each section of this directory, products are listed by increasing carbon content. Rieke® Highly Reactive Metals If viewing the electronic version simply select Grignard Reagents a category to jump to that section or activate Alkyl Alkenyl Alkynyl Aryl Heteroaryl your Adobe Bookmarks. You may also search by name, product number, molecular formula, Organozinc Halides or CAS registry number simply by using the “find” feature in Adobe (Ctrl+F in Windows or Alkyl Alkenyl Aryl Heteroaryl Introduction Command+F in a Mac environment). Dialkylmagnesium and Dialkylzinc Reagents If you are unable to find a reagent for your research “Please Bother Us” at [email protected], or contact your local Sigma-Aldrich office (see back cover). Foreword Reuben D. Rieke President and CEO, Rieke Metals, Inc. Professor Emeritus, University of Nebraska Lincoln, NE In the last 35 years, considerable research has been done in the area of generating reactive metals that can be used to synthesize novel organometallic reagents. In 1972, we reported a general approach for preparing highly reactive metal powders, relying on the reduction of metal salts with alkali metals in ethereal or hydrocarbon solvents. -
SAFETY DATA SHEET Santa Cruz Biotechnology, Inc
SAFETY DATA SHEET Santa Cruz Biotechnology, Inc. Revision date 05-Apr-2018 Version 1 1. IDENTIFICATION OF THE SUBSTANCE/PREPARATION AND OF THE COMPANY/UNDERTAKING _____________________________________________________________________________________________________________________ Product identifier Product Name Methyl-d3-magnesium iodide solution Product Code SC-235856 Recommended use of the chemical and restrictions on use For research use only. Not intended for diagnostic or therapeutic use. Details of the supplier of the safety data sheet Emergency telephone number Chemtrec Santa Cruz Biotechnology, Inc. 1.800.424.9300 (Within USA) 10410 Finnell Street +1.703.527.3887 (Outside USA) Dallas, TX 75220 831.457.3800 800.457.3801 [email protected] 2. HAZARDS IDENTIFICATION _____________________________________________________________________________________________________________________ This chemical is considered hazardous by the 2012 OSHA Hazard Communication Standard (29 CFR 1910.1200). Classification Acute toxicity - Oral Category 4 Specific target organ toxicity (single exposure) Category 3 Substances or mixtures which, in contact with water, emit Category 1 flammable gases Flammable liquids Label elements Signal word Danger Hazard statements Harmful if swallowed May cause drowsiness or dizziness Extremely flammable liquid and vapor In contact with water releases flammable gases which may ignite spontaneously Symbols/Pictograms Precautionary Statements - Prevention Wash face, hands and any exposed skin thoroughly after handling Do not eat, drink or smoke when using this product Avoid breathing dust/fume/gas/mist/vapors/spray Use only outdoors or in a well-ventilated area Keep away from heat/sparks/open flames/hot surfaces. — No smoking Keep container tightly closed Ground/bond container and receiving equipment Use only non-sparking tools Take precautionary measures against static discharge Wear protective gloves/protective clothing/eye protection/face protection Handle under inert gas. -
Chemical Name Federal P Code CAS Registry Number Acutely
Acutely / Extremely Hazardous Waste List Federal P CAS Registry Acutely / Extremely Chemical Name Code Number Hazardous 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- P059 76-44-8 Acutely Hazardous 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-, 3-oxide P050 115-29-7 Acutely Hazardous Methanimidamide, N,N-dimethyl-N'-[2-methyl-4-[[(methylamino)carbonyl]oxy]phenyl]- P197 17702-57-7 Acutely Hazardous 1-(o-Chlorophenyl)thiourea P026 5344-82-1 Acutely Hazardous 1-(o-Chlorophenyl)thiourea 5344-82-1 Extremely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extremely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extremely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extremely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extremely Hazardous 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,8- dimethanonaph-thalene Extremely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extremely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extremely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extremely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime. -
Experiment 12 Grignard Reaction; Preparation of Triphenylcarbinol
Experiment 12 Grignard Reaction; Preparation of Triphenylcarbinol In this experiment we will perform a Grignard addition to an ester. First we will form the Grignard reagent from magnesium and bromobenzene and then we will add it to methyl benzoate to produce triphenylcarbinol (also called triphenylmethanol). The overall sequence is shown in Figure 12.1 and the mechanism for the addition is shown in Figure 12.2. Figure 12.1 Grignard Addition to Methyl benzoate Br MgBr + Mg THF warm bromobenzene phenylmagnesium bromide O OMgBr OH C MgBr C C HCl OCH + MgBr(OH) 2 + 3 H2O methyl benzoate Triphenylcarbinol Since we are using an ester as our electrophile in this reaction, the nucleophilic Grignard reagent, prepared from the bromobenzene and magnesium, will add to the carbonyl two times to give the triphenyl adduct that on treatment with aqueous acid gives the free alcohol. Note that we have a ketone intermediate. This is even more reactive than the starting ester (why?) and reacts again with the Grignard reagent. Figure 12.2 Mechanism for Grignard Addition MgBr+ O O O OCH3 C C BrMg C OCH + -OCH 3 + 3 MgBr OH OMgBr HCl MgBr(OH) + C C H2O Physical Constants Compound Mol. Wt (g/mol) Density b.p. (°C) m.p. (°C) (g/mL) Bromobenzene 157.02 1.491 156 -31 Methyl benzoate 136.15 1.094 198-199 -12 Magnesium 24.31 1.740 - 648 Triphenylcarbinol 260.34 solid 360 160-163 Tetrahydrofuran (THF) 72.11 0.889 65-67 -108 Procedure: The set-up for this experiment is shown in Figure 12.3. -
University Microfilms, Inc., Ann Arbor, Michigan MONOMERIC ORGANOSILICON COMPOUNDS
This dissertation has been . micro&hned exactly as received 66-3860 CHAPMAN, Dwain R, 1929- MONOMERIC ORGANOSnJCON COMPOUNDS WITH POLYFUNCTIONAL GROUPS. Iowa State University of Science and Technology Ph.D., 1965 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan MONOMERIC ORGANOSILICON COMPOUNDS . WITH POLYPUNCTIONAL GROUPS by Dwain R Chapman A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved Signature was redacted for privacy. In Chai^ge of Major Work Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1965 11 TABLE OP CONTENTS' Page INTRODUCTION , 1 NOMENCLATURE 3• HISTORICAL 5 Cyclosilanes 5 Reactions of Cyclosilanes 6 Reactions of the Silicon-Silicon Bond 12 The Ultraviolet Absorption Properties 21 of Polysilanes Heterocyclic Polysilanes 23 . EXPERIMENTAL 28 Preparation of Cyclosilanes 30 Octaphenylcyclotetrasilane. 30 Decaphenylcyclopentasilane (Ila) 31 Dodecamethylcyclohexasilane 32 % Reactions of Octaphenylcyclotetrasilane 33 Octaphenylcyclotetrasilane with 33 , . phosphorus pentachloride In benzene 33 Tn xylene 33 Octaphenylcyclotetrasilane with 34 phosphorus trichloride (attempted). Octaphenylcyclotetrasilane with . 34 chlorine In carbon tetrachloride 34 In ether 34 In petroleum ether (b.p. 60-70 C) 36 In n-pentane 36 In ether containing hydroquinone ' 36 Ill Octaphenylcyclotetrasllane -
IODINE Its Properties and Technical Applications
IODINE Its Properties and Technical Applications CHILEAN IODINE EDUCATIONAL BUREAU, INC. 120 Broadway, New York 5, New York IODINE Its Properties and Technical Applications ¡¡iiHiüíiüüiütitittüHiiUitítHiiiittiíU CHILEAN IODINE EDUCATIONAL BUREAU, INC. 120 Broadway, New York 5, New York 1951 Copyright, 1951, by Chilean Iodine Educational Bureau, Inc. Printed in U.S.A. Contents Page Foreword v I—Chemistry of Iodine and Its Compounds 1 A Short History of Iodine 1 The Occurrence and Production of Iodine ....... 3 The Properties of Iodine 4 Solid Iodine 4 Liquid Iodine 5 Iodine Vapor and Gas 6 Chemical Properties 6 Inorganic Compounds of Iodine 8 Compounds of Electropositive Iodine 8 Compounds with Other Halogens 8 The Polyhalides 9 Hydrogen Iodide 1,0 Inorganic Iodides 10 Physical Properties 10 Chemical Properties 12 Complex Iodides .13 The Oxides of Iodine . 14 Iodic Acid and the Iodates 15 Periodic Acid and the Periodates 15 Reactions of Iodine and Its Inorganic Compounds With Organic Compounds 17 Iodine . 17 Iodine Halides 18 Hydrogen Iodide 19 Inorganic Iodides 19 Periodic and Iodic Acids 21 The Organic Iodo Compounds 22 Organic Compounds of Polyvalent Iodine 25 The lodoso Compounds 25 The Iodoxy Compounds 26 The Iodyl Compounds 26 The Iodonium Salts 27 Heterocyclic Iodine Compounds 30 Bibliography 31 II—Applications of Iodine and Its Compounds 35 Iodine in Organic Chemistry 35 Iodine and Its Compounds at Catalysts 35 Exchange Catalysis 35 Halogenation 38 Isomerization 38 Dehydration 39 III Page Acylation 41 Carbón Monoxide (and Nitric Oxide) Additions ... 42 Reactions with Oxygen 42 Homogeneous Pyrolysis 43 Iodine as an Inhibitor 44 Other Applications 44 Iodine and Its Compounds as Process Reagents ...