DOCSLIB.ORG

University of Oklahoma Graduate College Survey

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
University of Oklahoma Graduate College Survey UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE SURVEY OF CATALYST AND REDUCTANT EFFECTS ON OXORHENIUM CATALYZED DEOXYDEHYDRATION OF GLYCOLS A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY By JAMES MICHAEL MCCLAIN II Norman, Oklahoma 2015 SURVEY OF CATALYST AND REDUCTANT EFFECTS ON OXORHENIUM CATALYZED DEOXYDEHYDRATION OF GLYCOLS A DISSERTATION APPROVED FOR THE DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY BY ______________________________ Dr. Kenneth M. Nicholas, Chair ______________________________ Dr. Robert P. Houser ______________________________ Dr. George Richter-Addo ______________________________ Dr. Robert K. Thomson ______________________________ Dr. Ronald L. Halterman ______________________________ Dr. Lee R. Krumholz © Copyright by JAMES MICHAEL MCCLAIN II 2015 All Rights Reserved. To my parents & sisters for a lifetime of love, support, and faith in my shenanigans, thank you. Acknowledgements I would not have made it to where I am today without the friendship, mentorship, encouragement, and support of countless people. I know I cannot adequately thank everyone responsible for influencing me to develop into the person I am today and I will inevitably leave out many who deserve recognition, to those individuals I apologize and greatly thank you. As a child, while working in my grandpa’s workshop he would always tell me “can’t ain’t a word” anytime I said I couldn’t do one thing or another. At the time I thought, ironically, he was giving me a grammatical lesson, it wasn’t till after his passing and I was older that I truly understood what he was telling me. This has become my general philosophy in life when challenges present themselves; I concede that it occasionally leads me to pursue endeavors off the main track but I owe most of my accomplishments to this stubbornness. Of course, my parents and sisters are responsible for much of whom I am and have been a part of all that I have done. My friends have been a second family and have grown too numerous to thank them all for the good times and support but I am greatly appreciative. I have to mention some of my closest friends, Robert, Anna, Katie, and Camille for years of fun, listening to me complain about trivial things, and the motivation to keep moving forward. Thank you to my teachers and mentors all through my life. Particularly my grade school advanced program instructor Ms. Schaflein for encouraging me to think independently and abstractly. I am grateful to all my research mentors, Dr. Tim Hubin, Dr. Bob Houser, and Dr. Ken Nicholas for all that I learned from them, their inspiration, and individual perspectives. iv Table of Contents Acknowledgements ..................................................................................................... iv Table of Contents ..........................................................................................................v List of Tables .............................................................................................................. ix List of Figures ............................................................................................................. xi Abstract .................................................................................................................... xvii Chapter 1 Biomass, a Renewable Carbon Source ....................................................1 1.1 Dependence on Fossil-Based Resources .......................................................2 1.2 Sustainable Energy and Chemical Feedstocks ..............................................4 1.3 Utilization of Cellulosic Biomass .................................................................5 1.4 Conversions of Biomass Derived Sugars and Polyols ...................................8 1.5 Deoxydehydration (DODH) ....................................................................... 10 Chapter 2 Elemental Reductants in the Deoxydehydration of Polyols ................... 25 2.1 Background and Introduction ..................................................................... 26 2.2 Exploratory Reactions with the Activated Substrate DET ........................... 28 2.3 Aliphatic Glycols ....................................................................................... 29 2.4 Reflux Reactions ........................................................................................ 31 2.5 Electronically Different Substrates ............................................................. 32 2.6 Mass Balance for High Conversion/Moderate Yield Reactions ................... 34 2.7 Discussion ................................................................................................. 41 2.8 Conclusion ................................................................................................. 42 2.9 Experimental .............................................................................................. 43 2.9.1 Reagents .............................................................................................. 43 v 2.9.2 Typical Reaction Conditions ................................................................ 43 2.9.3 Notes on Elemental Metals ................................................................... 44 2.9.4 Instrumentation .................................................................................... 45 2.9.5 Quantification Procedures .................................................................... 45 2.9.6 Standard Reaction ................................................................................ 47 2.9.7 Procedure testing for CO and CO2 ........................................................ 48 Chapter 3 Oxorhenium(V) Catalyzed DODH ....................................................... 50 3.1 Background and Introduction ..................................................................... 51 3.2 Synthesis of Trans-[ReO2py4]Cl (1a) ......................................................... 53 3.3 Establishing Catalytic Activity of [ReO2py4]Cl (1a) for DODH with Glycols and Sodium Sulfite ..................................................................................... 54 3.4 Benzyl Alcohol as Reductant ..................................................................... 61 3.5 Nature of Oxorhenium Catalyst in Reaction/Post-Reaction......................... 64 + 3.6 Investigating the Activity of trans-[ReO2py4] in Additional DODH Reactions ................................................................................................... 65 + 3.7 Elemental Reductants for trans-[ReO2py4] catalyzed DODH. ................... 69 3.8 ReO2(TPP)2I (2) as a DODH Catalyst ........................................................ 70 3.9 Conclusions ............................................................................................... 72 3.10 Experimental .............................................................................................. 73 3.10.1 Reagents .............................................................................................. 73 3.10.2 Instrumentation and Analytical Methods .............................................. 74 3.10.3 Typical DODH Reaction Conditions .................................................... 74 3.10.4 Quantification ...................................................................................... 75 vi 3.10.5 Standard Reaction ................................................................................ 75 3.10.6 Mass Spectrometric Experiment Described in Section 3.5 .................... 76 Chapter 4 Mechanistic Studies of Oxorhenium-Catalyzed DODH ........................ 77 4.1 Background and introduction ..................................................................... 78 4.2 Initial reaction time course experiments ..................................................... 82 4.3 Establishing standard reaction conditions and stoichiometry effects ........... 84 4.4 Substituted pyridine analogs of the type [ReO2(4-X-py)4]PF6 ..................... 90 4.5 Observed effect of added pyridine or triphenylphosphine oxide to the [ReO2py4]PF6/BnOH/1,2-decanediol DODH reaction ................................ 92 4.6 Kinetic isotope effect with singly and doubly benzylic deuterium labeled BnOH ........................................................................................................ 93 4.7 Stoichiometric reactions ............................................................................. 97 4.8 Conclusions ............................................................................................. 105 4.9 Experimental ............................................................................................ 107 4.9.1 Reagents ............................................................................................ 107 4.9.2 Instrumentation .................................................................................. 110 4.9.3 Typical Catalytic DODH Reaction Conditions ................................... 111 4.9.4 Quantification .................................................................................... 111 + 4.9.5 ESI-MS of ethylene glycol/[ReO2py4] ............................................... 112 4.9.6 Rhenium calculations ......................................................................... 113 Chapter 5 Project Summary and Future Directions ............................................. 117 5.1 Project summary .....................................................................................
Load more

Recommended publications
  • A Contribution to the Chemistry of Rhenium
    U. S. DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS RESEARCH PAPER RP999 Part of Journal of Research of the J'Xational Bureau of Standards, Volume 18, May 1937 A CONTRIBUTION TO THE CHEMISTRY OF RHENIUM . By C. E. F. Lundell and H. B. Knowles ABSTRACT A study of the behavior of rhenium when dilute solutions of potassium per­ rhenate are acidified with sulphuric acid, cooled, and passed through the Jones reductor, indicates that rhenium forms a compound in which it has a valency of minus one, and that the rhenium in this compound is oxidized to a valency of plus one if the diluted sulphuric acid solution is protected from oxygen and warmed to approximately 50° C. In the course of the investigation, it was also found (1) that rhenium can be electrodeposited from diluted (5+95) sulphuric acid solution; (2) that deposits are slightly contaminated; and (3) that the deposited metal can be oxidized directly to perrhenic acid by exposure to moist air, oxygen, or by making the deposit the anode in a water solution. CONTENTS Page 1. Introduction ___ _____________________ ____ __ __ _____ ___ ___ _____ _____ 629 II. ExperimentaL _ ___ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ __ ___ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 630 1. Reagents, reductor, and reductor technique ___________________ 630 2. Oxidation of the reduced compound _______________ ___________ 631 3. Potentiometric titrations _______________ ___ ___ ______ ___ _____ 634 4.
    [Show full text]
  • Simulating the Micro Uidic Solvent Extraction of Perrhenate
    Simulating the microfluidic solvent extraction of perrhenate Investigating the influence of pH and leakage by Miranda van Duijn to obtain the degree of Bachelor of Science at the Delft University of Technology, to be defended publicly on Tuesday January 23, 2018 at 10:00 AM. Student number: 4355776 Project duration: September, 2017 – January 23, 2018 Thesis committee: Ir. Z. Liu, TU Delft, supervisor Dr. ir. M. Rohde, TU Delft Prof. dr. ir. J.L. Kloosterman TU Delft Abstract Several of the researches conducted at the Reactor Institute Delft (RID) concern the extraction process of perrhenate, ReO4¡. From the perrhenate, rhenium-188 (Re-188) is obtained. Re-188 is medically useful as a high energy ¯ emitter. It can be used as an imaging agent, for in situ tumor treatment and biodistribution. Re-188 is produced via commercially available 188W /188Re radionuclide generators, which have proved their usefulness as a conventional product. Via the production with this generator, the ReO4¡ resides in an aqueous solution together with other compounds such as tungsten-188 (W-188). To medically use the ReO4¡, it needs to be of a certain degree of radionuclidic purity, the proportion of the total radioactivity that is present as a specific radionuclide. [1] A relatively new method to extract the ReO4¡ from the aqueous solution into a liquid organic phase might be microfluidic solvent extraction. This principle is based on the laminar coflowing of two liquid immisci- ble phases between which an interface develops. The ReO4¡ is then transferred through the interface, thus leading to an extraction. Microfluidic solvent extraction offers several inherent advantages, such as the high surface-to-volume ra- tio and short diffusion distances.
    [Show full text]
  • Cyclotron Produced Radionuclides: Guidelines for Setting up a Facility, Technical Reports Series No
    f f f IAEAIAEA RADIOISOTOPESRADIOISOTOPES ANDAND RADIOPHARMACEUTICALSRADIOPHARMACEUTICALS REPORTSREPORTS NNo.. 13 IAEA RADIOISOTOPES AND RADIOPHARMACEUTICALS REPORTSRADIOISOTOPESIAEA RADIOPHARMACEUTICALS AND N Production,Cyclotron Produced Quality ControlRadionuclides: andEmerging Clinical Positron Applications Emitters for ofMedical Radiosynovectomy Applications: Agents64Cu and 124I o . 3 . Atoms for Peace INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA Atoms for Peace Atoms for Peace IAEA RADIOISOTOPES AND Atoms for Peace RADIOPHARMACEUTICALS SERIES PUBLICATIONS One of the main objectives of the IAEA Radioisotope Production and Radiation Technology programme is to enhance the expertise and capability of IAEA Member States in deploying emerging radioisotope products and generators for medical and industrial applications in order to meet national needs as well as to assimilate new developments in radiopharmaceuticals for diagnostic and therapeutic applications. This will ensure local availability of these applications within a framework of quality assurance. Publications in the IAEA Radioisotopes and Radiopharmaceuticals Series provide information in the areas of: reactor and accelerator produced radioisotopes, generators and sealed sources development/production for medical and industrial uses; radiopharmaceutical sciences, including radiochemistry, radiotracer development, production methods and quality assurance/ quality control (QA/QC). The publications have a broad readership and are aimed at meeting the needs of scientists, engineers,
    [Show full text]
  • I. an Improved Procedure for Alkene Ozonolysis. II. Exploring a New Structural Paradigm for Peroxide Antimalarials
    University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Student Research Projects, Dissertations, and Theses - Chemistry Department Chemistry, Department of 2011 I. An Improved Procedure for Alkene Ozonolysis. II. Exploring a New Structural Paradigm for Peroxide Antimalarials. Charles Edward Schiaffo University of Nebraska-Lincoln Follow this and additional works at: https://digitalcommons.unl.edu/chemistrydiss Part of the Organic Chemistry Commons Schiaffo, Charles Edward, "I. An Improved Procedure for Alkene Ozonolysis. II. Exploring a New Structural Paradigm for Peroxide Antimalarials." (2011). Student Research Projects, Dissertations, and Theses - Chemistry Department. 23. https://digitalcommons.unl.edu/chemistrydiss/23 This Article is brought to you for free and open access by the Chemistry, Department of at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Student Research Projects, Dissertations, and Theses - Chemistry Department by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. I. An Improved Procedure for Alkene Ozonolysis. II. Exploring a New Structural Paradigm for Peroxide Antimalarials. By Charles E. Schiaffo A DISSERTATION Presented to the Faculty of The Graduate College at the University of Nebraska In Partial Fulfillment of Requirements For the Degree of Doctor of Philosophy Major: Chemistry Under the Supervision of Professor Patrick H. Dussault Lincoln, Nebraska June, 2011 I. An Improved Procedure for Alkene Ozonolysis. II. Exploring a New Structural Paradigm for Peroxide Antimalarials. Charles E. Schiaffo, Ph.D. University of Nebraska-Lincoln, 2011 Advisor: Patrick H. Dussault The use of ozone for the transformation of alkenes to carbonyls has been well established. The reaction of ozone with alkenes in this fashion generates either a 1,2,4- trioxolane (ozonide) or a hydroperoxyacetal, either of which must undergo a separate reduction step to provide the desired carbonyl compound.
    [Show full text]
  • Technetium Chemistry, Oxidation States and Species
    J. inorg, nucl. Chem., 1967, Vol, 29, pp. 681 to 691. PergamonPress Ltd. Printedin NorthernIreland TECHNETIUM CHEMISTRY, OXIDATION STATES AND SPECIES C. L. RULFS, R. A. PACER and R. F. HIRSCH Department of Chemistry, The University of Michigan, Ann Arbor, Michigan (Recewed14July1966) Abstraet--Pertechnetic and perrhenic acids behave as very strong acids, Ka ,~ l0 s. Their extensive dehydration to MzO7 in such media as 7 M sulphuric acid complicates a spectrophotometric com- parison of acid strengths. Chloroform extractable TcO~C1 forms from pertechnetate in the presence of chloride ion and concentrated sulphuric acid. The (VII) state of this compound is confirmed and its spectrum described. No evidence of unusual technetium (VII) species, in aqueous media of 1 N base to 1 N acid, has been found. The red colour of concentrated aqueous HTcO4 is ascribed to a lower (VI) or (V) state. The existence in alkaline media of a technetate, TcOsg-, species has been re-examined. Some (IV) and (III) state species are partially characterized, but no Tc~Os could be isolated. INTRODUCTION WHILS the chemistry of technetium closely parallels that of rhenium, any distinctions of behaviour in the sequence Mn-Tc-Re are of great interest. A chronological comparison of recent summaries of technetium chemistry(1-5) shows this to be a rather active area of study. The results of the present study are described in sections associated with species and oxidation states. The conventional techniques and equipment employed are described very concisely. Further detail is available in two recent theses. (6'7) EXPERIMENTAL Reagents. All technetium-99 material was obtained from the Oak Ridge National Laboratory, either as technetium metal powder or as ammonium pertechnetate solutions.
    [Show full text]
  • THE PREPARATION of a SOLID RHENIDE by Justo B. Bravo B. S
    THE PREPARATION OF A SOLID RHENIDE by Justo B. Bravo B. S. Ch. E., Adamson University Manila, Philippines, 1940 Submitted to the Department of Chemistry and the Faculty of the Graduate School of the University of Kansas 1n partial fulfillment of the requirements for the degree of Doctor of Philosophy. Advisory Committee: Redacted Signature --~--#'·----·-·- ----··-- ----·-- -· ---z._.-- - Chairman 6 . Redacted Signature >< -· ·r >< - -y .... .'-""V "--. Redacted Signature -:;----~-· ~-----· T --- -----· .~ • - • -- ,,,.. -- _. - - ./ Redacted Signature ··ryy l,~ J a.nua.ry, 19 53 Acknowledgement The autho~ wishes to express his sincere appreciation to Dr. Jacob Klein.berg and to Dr. Ernest Griswold for their con- stant encouragement and advice during the course of this work. Thanlts are also due my wife, Aurora, whose understanding ha.s made this work possible. Special thanks are due the Office .of Naval Research for their financial support of this investigation. · TABLE OF CONTENTS I. INTRODUCTION •.•• . l II. HISTORICAL REVIEW 3 III. EXPERIMENTAL • • 9 A. Materials .••. 9 B. Analytical Methods . 10 1. ·Determination of water content of ethylenediamine. 2. Measurement of reducing power of the rhenide compound. 3. Rhenium analysis. 4. Potassium analysis. c. The Reduction of Potassium Perrhenate. 17 l. Preliminary work. 2. Red_uction. of potassium perrhenate with potassium in ethylenediamine- water solutions. 3. Some properties of the white solid. D. The Separation of Potassium Rhe.nide. 29 1. Preliminary work. 2. Extraction of potassium hyd.roxide by isopropyl alcohol. 3~ Analysis of the final product. E. Ma£netic Susceptibility Measurements •• 44 F. Some Properties, of Potassium Rhenide Tetra.hydrate . • 50 IV. Stflvll-'.LARY • . 51 v. SUGGESTIONS FOR FUTURE WORK • .
    [Show full text]
  • The Radiochemistry of Rhenium COMMITTEE on NUCLEAR SCIENCE
    Na?ional Academy of Sciences PJational Research Council 9 NUCLEAR SCIENCE SERIES The Radiochemistry of Rhenium COMMITTEE ON NUCLEAR SCIENCE L. F. CURTISS, Chuirman ROBLEY D. EVANS, Vice Chairman National Bureau of Standards Massachusetts Instituteof Technology J. A. DsJUREN, Secyetiwy Westinghouse Electric Corporation C. J. BORKOWSKI J. W. IRVINE, JR. Oak Ridge National Laboratory Massachusetts Instituteof Technology ROBERT G. COCHIUN E. D. KLEMA Texaa Agricultural and Mecbanioal Northwestern UniverslW College W. WAYNE MEINKE University of Michigan SAMUEL EPSTEIN California Institute of Technology J. J. NICKSON Memorial Hospital, New York U. FANO National Bureau of Standarda ROBERT L. PLATZMAN Laboratctre de Chimie Physique HERBERT GOLDSTEIN Nuclear Development Corporation of D. M. VAN PATTER America Bartol Research Foundation LIAISON MEMBERS PAUL C. AEBERSOLD CHARLES K. REED Atomic Energy Commission U. S. Air Force J. HOWARD McMILLEN WILLIAM E. WRIGHT National Science Foundation Office of Naval Researoh SUBCOMMlllEE ON RADIOCHEMISTRY W. WAYNE MEINKE, Chairman HAROLD KfRBY University of Michigan Mound Laboratory GREGORY R. CHOPPIN GEORGE LEDDICOTTE Florida State Unlversi~ Oak Ridge National Laboratory GEORGE A. COWAN JULIAN NIELHEN Los Alarnos Sclentiflc Laboratory Hanfofi Laboratories ARTHUR W. FAIRHALL ELLIS P. STEINBERG IJniverslty of Washington Argonne National Laboratory JEROME HUDIS PETER C, STEVENSON Brcdhaven National Labcmtory University of California (Liverrnore) EARL HYDE LEO YAFFE University of California (Berkeley) McGill University CONSULTANTS NA THAN BALLOU JAMES DeVOE Centre d’Etude de l’Euy@e Nucleaire University of Miohigsn Mol-Donk, Belgiugi’ . WILLIAM MARLOW National Bureau of Standards CHEMISTRY The Radiochemistry of Rhenium G. W.” LEDDICOTTE Analytical Chemistry Division Oak Ridge National Laboratory Oak Ridge, Tennessee Fwuanc-sDate:April1981 Subcommittee on Radiochemistry National Academy of Sciences —National Research Council Printedin USA.Price$0.50.AvailablefromtbeOfficeofTechnical Services,DepartmentofCommerce.Washington25,D.C.
    [Show full text]
  • Chemical Names and CAS Numbers Final
    Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number C3H8O 1‐propanol C4H7BrO2 2‐bromobutyric acid 80‐58‐0 GeH3COOH 2‐germaacetic acid C4H10 2‐methylpropane 75‐28‐5 C3H8O 2‐propanol 67‐63‐0 C6H10O3 4‐acetylbutyric acid 448671 C4H7BrO2 4‐bromobutyric acid 2623‐87‐2 CH3CHO acetaldehyde CH3CONH2 acetamide C8H9NO2 acetaminophen 103‐90‐2 − C2H3O2 acetate ion − CH3COO acetate ion C2H4O2 acetic acid 64‐19‐7 CH3COOH acetic acid (CH3)2CO acetone CH3COCl acetyl chloride C2H2 acetylene 74‐86‐2 HCCH acetylene C9H8O4 acetylsalicylic acid 50‐78‐2 H2C(CH)CN acrylonitrile C3H7NO2 Ala C3H7NO2 alanine 56‐41‐7 NaAlSi3O3 albite AlSb aluminium antimonide 25152‐52‐7 AlAs aluminium arsenide 22831‐42‐1 AlBO2 aluminium borate 61279‐70‐7 AlBO aluminium boron oxide 12041‐48‐4 AlBr3 aluminium bromide 7727‐15‐3 AlBr3•6H2O aluminium bromide hexahydrate 2149397 AlCl4Cs aluminium caesium tetrachloride 17992‐03‐9 AlCl3 aluminium chloride (anhydrous) 7446‐70‐0 AlCl3•6H2O aluminium chloride hexahydrate 7784‐13‐6 AlClO aluminium chloride oxide 13596‐11‐7 AlB2 aluminium diboride 12041‐50‐8 AlF2 aluminium difluoride 13569‐23‐8 AlF2O aluminium difluoride oxide 38344‐66‐0 AlB12 aluminium dodecaboride 12041‐54‐2 Al2F6 aluminium fluoride 17949‐86‐9 AlF3 aluminium fluoride 7784‐18‐1 Al(CHO2)3 aluminium formate 7360‐53‐4 1 of 75 Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number Al(OH)3 aluminium hydroxide 21645‐51‐2 Al2I6 aluminium iodide 18898‐35‐6 AlI3 aluminium iodide 7784‐23‐8 AlBr aluminium monobromide 22359‐97‐3 AlCl aluminium monochloride
    [Show full text]
  • Download Safety Data Sheet
    CMI Product #1022 Issued 06/15/15 Safety Data Sheet 29 CFR 1910.1200 Section 1: Company and Product Identification Product Name: Sodium perrhenate Product Code: 1022 Company: Colonial Metals, Inc. Building 20 505 Blue Ball Road Elkton, MD 21921 United States Company Contact: EHS Director www.colonialmetals.com Telephone Number: 410-398-7200 FAX Number: 410-398-2918 E-Mail : [email protected] Web Site: www.colonialmetals.com Emergency Supplier Emergency Contacts & Phone Number Response: Chemtrec: 800-424-9300 World Wide - Call COLLECT to U.S: 703-527-3887 Section 2: Hazards Identification GHS07 GHS03 BLANK BLANK Hazard Pictograms: Signal Word: Warning Hazard Category: Serious eye damage/eye irritation Cat 2 Skin corrosion/irritation Cat 2 Specific target organ tox, single exp. Cat 3 (resp irrit) Oxidizer Cat 2 Hazard Statements: H319: Causes serious eye irritation H315: Causes skin irritation H335: May cause respiratory irritation H272: May intensify fire; oxidizer Precautionary P202: Do not handle until all safety precautions have been read and understood Statements: P210: Keep away from heat/sparks/open flames/hot surfaces – No smoking P264: Wash thoroughly after handling P280: Wear protective gloves/protective clothing/eye protection/face protection P305+351+338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present and easy to do – continue rinsing P402+404: Store in a dry place. Store in a closed container P501: Dispose of contents/container in accordance with local/national/international rules. Not applicable, none known. The toxicological properties of this material have not been Hazards not fully investigated. This product is considered non-hazardous when evaluated by criteria otherwise classified: established in the OSHA Hazard Communication Standard (29 CFR 1910.1200).
    [Show full text]
  • Heterogeneous Catalytic Reduction of Perchlorate in Water
    Heterogeneous Catalytic Reduction of Perchlorate in Water Keith D. Hurley Final Seminar September 19, 2008 - The perchlorate ion, ClO4 , is today widely regarded as a contaminant of ground and surface waters, as well as soil, throughout the United States, with over 400 recognized contaminated sites in 35 states [1]. The chemistry of perchlorate is dominated entirely by kinetics, and its high kinetic barrier to reduction makes it effectively inert to reduction by typical nucleophilic reducing agents or to complexation [2-4]. The argument for perchlorate remediation is based on its known interference with normal thyroid function [5]. The cause of this interference is the preferential uptake of perchlorate over iodide by the thyroid [6]. It is well established that the thyroid regulates neural development in fetuses and infants [7]. Current perchlorate remediation strategies are largely limited to ion exchange (IX) or bioremediation [8, 9]. In 1995 Abu-Omar and Espenson [10] showed that a rhenium(V) complex in aqueous solution, formulated as methylrhenium dioxide (MDO), can react relatively rapidly with perchlorate by an oxygen atom transfer (OAT) reaction to form an rhenium(VII) complex (methylrhenium trioxide, MTO) and chlorate. The cycle could be closed by reducing the Re(VII) complex back to the Re(V) complex with hypophosphorous acid (H3PO2) [11]. Such a homogeneous catalyst with a soluble phosphorus or sulfur reducing agent is not readily compatible with water purification systems. In an effort to make a catalytic system more compatible with water treatment a heterogeneous catalyst has been developed that promotes the reduction by hydrogen of perchlorate ion in water under mild conditions.
    [Show full text]
  • (VII) Oxide As a Catalyst for the Substution of Hemiacetals
    University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Student Research Projects, Dissertations, and Theses - Chemistry Department Chemistry, Department of Fall 11-29-2012 The Use of Rhenium (VII) Oxide as a Catalyst for the Substution of Hemiacetals Michael W. Richardson University of Nebraska-Lincoln, [email protected] Follow this and additional works at: https://digitalcommons.unl.edu/chemistrydiss Part of the Organic Chemistry Commons Richardson, Michael W., "The Use of Rhenium (VII) Oxide as a Catalyst for the Substution of Hemiacetals" (2012). Student Research Projects, Dissertations, and Theses - Chemistry Department. 37. https://digitalcommons.unl.edu/chemistrydiss/37 This Article is brought to you for free and open access by the Chemistry, Department of at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Student Research Projects, Dissertations, and Theses - Chemistry Department by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. THE USE OF RHENIUM (VII) OXIDE AS A CATALYST FOR THE SUBSTITUTION OF HEMIACETALS By Michael W. Richardson A THESIS Presented to the Faculty of The Graduate College at the University of Nebraska In Partial Fulfillment of Requirements For the Degree of Master of Science Major: Chemistry Under the Supervision of Patrick H. Dussault Lincoln, Nebraska November, 2012 THE USE OF RHENIUM (VII) OXIDE AS A CATALYST FOR THE SUBSTITUTION OF HEMIACETALS Michael W. Richardson, M.S. University of Nebraska, 2012 Adviser: Patrick H. Dussault Rhenium (VII) oxides have proven to be mild and versatile catalysts in organic chemistry. They have previously been utilized to catalyze the transposition of allylic aclohols, Prins reaction, and reductive amination to name a few examples.
    [Show full text]
  • Bis(Triphenylphosphine)Gold(I) Perrhenate
    Bis(triphenylphosphine)gold(I) Perrhenate Sebastian A. Baera, Alexander Pothig¨ a, Salem M. Bawakedb, Hubert Schmidbaura;b, and Florian Krausa a Department Chemie, Technische Universitat¨ Munchen,¨ 85747 Garching, Germany b Chemistry Department, King Abdulaziz University, Jeddah 21589, Saudi Arabia Reprint requests to PD Dr. F. Kraus E-mail: fl[email protected] and Prof. Dr. H. Schmidbaur [email protected] Z. Naturforsch. 2013, 68b, 1173 – 1179 / DOI: 10.5560/ZNB.2013-3223 Received August 13, 2013 Dedicated to Professor Bernd Krebs on the occasion of his 75th birthday + − Bis(triphenylphosphine)gold(I) perrhenate [Ph3PAuPPh3] ReO4 has been prepared in high yield from Ph3PAuCl, Ph3P and AgReO4 in a mixed solvent. The compound is stable in air and decomposes at 235 ◦C. In the crystal structure, the two independent perrhenate anions are not approaching the gold centers of the two independent cations, but weak interionic interactions are entertained via p-p stacking of phenyl groups and C–H···O contacts. As three-blade chiral rotors, the Ph3P ligands of the cations are in a staggered conformation at the gold atoms with only slightly bent P–Au–P axes. IR and NMR data show no anomalies and are close to those of alkali or onium perrhenates. Key words: Gold(I), Rhenate(VII), Crystal Structure, IR Spectra, Phosphine Introduction Covalently bonded perrhenates are rare and in most cases of limited stability [1–4]. This is particularly The non-coordinated tetrahedral uninegative per- true for simple perrhenic acid esters R–O–ReO3, in − rhenate anion ReO4 [1–4] is a component of many analogy to the (explosive) esters of perchloric and stable ionic solids where it appears surrounded by perbromic acid on the one hand, and of perman- a large variety of metal or onium cations [5– 18].
    [Show full text]