DOCSLIB.ORG

The Relative Reactivities of Some Organometallic Compounds

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
The Relative Reactivities of Some Organometallic Compounds Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1935 The elr ative reactivities of some organometallic compounds Kenneth E. Marple Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Marple, Kenneth E., "The er lative reactivities of some organometallic compounds " (1935). Retrospective Theses and Dissertations. 13644. https://lib.dr.iastate.edu/rtd/13644 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. UMI TiiS RELATIim REACTIVITIES OF SOME ORGAtiOliBTALLIO COflPOUIDS Kenneth E. Marple A Thesis Submitted to the Graduate Faculty for th© Degree of DOCTOR OF PHlLOSOPiH Major Subject Organic Chemistry ApprovedI Signature was redacted for privacy. In eiia'r^e oif Major work Signature was redacted for privacy. mm of Ma Signature was redacted for privacy. Dean of Graduate Gollegi"^' Iowa State College 19S5 UMI Number: DP12833 INFORMATION TO USERS 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 bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send 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. UMI UMI Microform DP12833 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 OiJA-n - g - n • AGKNOWLBDOSMENT fh© writer wishes to express iiis appreciation to Dr. Henrj Gilaea for the suggestion of tliis problem and for the generous advioa and enoooragement givexi during this work. "f 5 I 3 5 - 3 - , vf fABlJS OF GONTSIITS |, Page IHTRODUOTIOii 5 A. TliS COLOR TEST wiTIl ORGMOMSTALLIO COUPOmOS 9 lUTROBUOTION 9 EXPSRIMENTAL 12 DISCUSSION OF BSSULTS 18 mmmi 19 • B. QOm RBAGTIOHB OF OfiGMO-iL'tMIHUM GOMPOUNDS 20 IHTiiOi^ljaflOW 20 aXPEHIMEMT.iL 28 Beaotioa with Plieayl Isooyanate 26 Heaotioii with Garboii Dioxide 37 Heactioa with Benaophenon© 3B Reaotlon with Oxygen 38 Keaction with BenzaMehyde 38 Reac11 on witlx Benzoaitril© 39 Reaction with Esters 39 DISOUSSIOH Of HKSULTS 40 SmiAiii' 42 0. SmSi RSAOTIOKS OF ORGANQBOROn COMPOUHDS 43 INSRODUOl'ION 43 Ji;XI'i;;RIiIU,uTAL 51 Reaotion with Phenyl Isocyaaate 57 liQaotioa -with Benzaldeliyde 57 DISCUSSION Oj? RESULTS 59 SUKMaRY • 61 - 4 - Page 'D, tSOMii REACTIONS OF QBQANOZINO 00L5P0UNDS 62 IN'TROiWGTION 68 SXPSRIMSJSim 65 Beaotloii ifith Carbon Dioxide .......................... 67 Reaotion with [email protected] 67 Reaction with Phenyl Isooy-anate ....................... 68 Roaction with Benzonitrile 68 DISOTJSGICHJ OF RESITLTS 69 SIIMAI^Y 70 1. THE: RBLATIVB REAGTITITIES OF ORGAMOMSTALLIG 00:1?0U!IDS •OF ALUMIMUM, BOHyii AKD SING 71 Iim-iOOTOTION 71 SXPiSilMEMTAL 80 Keaatioa Bates with Miehler* s Ketone 84 Mlnimma Ooneentratioa Giving the Oolor Test ........... 87 Heaotion Rates with BeuzaMehyde, Benzophonone and Benzoaitrile 89 Bat© of Bisplaeerasnt of llerotiry froai Organomeroury Ooapounds by Aluminum aad Zino 93 DICGUSSION OF RiiSUL^IB . 95 SUMMIKY 99 5 - fHg RBLATra RSASTITITIES Of SOME QRGAMOMKTALLIO gOMPOUNDS Introduction Organic sjntiiesis is, in general, based upon the use of selectiw or preferential reactions. Organic chemistry is built upon the reaction of an organic compound with one or more other elements or coapounds, The success of any reaction depends to a large extent on the reactivities of the groups in­ volved, The ability to predict how a reaction will proceed or the best synthesis to us© in each case depends upon knowledge of the relative reaotivities of the compounds or groups involved. Organosetallic coapounds have often been used in reactions with polyfunctional compounds, fhus, Noller and Adams (1) by the proper use of a Grigaard reagent on aldehyde esters obtained compounds taat showed addition to the aldehyde group but not to the ester group. A large number (2) of such preferential reactions with polyfuactional compounds are found in the chemis­ try of organomagnesium coapounds. In some cases, however, preferential reaction does not take place as the Grignard reagent reacts equally well with all functional groups present. Thus, Boyd and Ladhams (3) hoped that by the use of preferential (liMoller and Adams, £. Am. Qhem. Soo.^ 48, 1074 (1926). (g| (a) Grignard, Oompt. rend.. 154. 849"Tl902)i (b) Fordyce and Johnson, £. Am.' d'hem. Soo., 55. 3368 (1933)'j (c) Mavrodin, Bui, soc. ohim. Reaaania. 15, 99 (19S3). (3) Boyd and Ladhams, j'l" '^hem. SOc. > 19S8« 2lfe9. — 6 ^ reaetion they could convert methyl o-oyaaobenzoate into o-cyano«« triphenylcarblnol. They found, however, that phenylmagneslum bromide in ether solution reacted with both the cyano and the ester groups. No trace of o-cyanotriphenylcarbinol could be detected. Finger and Gaul {4) report that in the reaction of Qrignard reagents on methyl ayanoformate both the ester and cyano groups were attacked by the Grignard reagent. It is hoped that by the use of organometallic compounds less reactive than the Grignard reagent preferential reactions of this type oan be carried out without difficulty. This may open new fields whereby other­ wise inaccessible compounds may be prepared through the medium of selective or preferential reactions involving organosetallie ooapounds less reactive than the Grignard reagents, Organonetallie compounds probably constitute the most impor­ tant group of compounds used in synthesis. They include all compounds which are characterized by the carbon-metal linkage and may be represented as falling into three ixaportant classes: first, those containing only like R groups attached to the metal; second, those having different H groups attached to the metalj and third, those having both R groups and halogen attached to the metal. The task of comparing the reactivities of all of these different compounds is great, and it is only through continued effort that it may be achieved, (4) Finger and Gaul, £. prakt. Chem., 111. 54 (1923). The proper method of approach in a study of this kind seems to be to attempt a correlation between the oheraical reactivities of the organometellic compound and the position of the metal in th© periodic table. Ifie raore reactive or- ganoaetallio compounds seem to be forraed from the metals in the lower left hand corner of the periodic table; that is, th© more positive the aietal the greefcer the reactivity, and the organorub idiura and organocesiuia compounds appear to be more reactiv® than. t>ios0 higher in the group (5). The orgaiioiQOtalliQ compounds of the second group ele- aents appesir to be less reectlve than the organoalkali com­ pounds (6), while the alltalln® earth metals end magnesium form the most active, organometallic compounds of the second group metals. In this studj an attempt has bean made to compare the relative rasotivity of the organometallic compounds of zinc of the second group olemonts witii tliose of aluminum and boron in the third group. Due to the wide range of reactivity of the many organometallic compounds, from the very reactive organoalkali compounds to the relatively stable orgsnocom- pounds of tin, bismuth and lead, it is difficult, if not impossible, to find any on© reaction which could be used in (5) For a genaral reviav and references saa: Julius Schraidt, •'Organoaetallverbindungen#" Stuttgart. 1934, (6) Oilman and ICirby, £. Am. Qhem. ^oc.. 55, 1265 (1933). a quantitative laanner to measure all tliair relatlTC reaction velocities or reaotivitiee. In the case of the three metals ohosen the reaetions entered into by all three are very fe^/. The raaetions of organoeluBiiama and -boron corapounds with Qoapomds coatainlng differeat functional groups have been little studi©d« Therefor©, it is first aQoessary to inves­ tigate the reaction of organoziac, -aluminum, and -boron ooiapounds with Qertain funetional groups and then to choose those best suited for a oomparison of the relative reactivities. A. 'ms OOLOH T3CT Wim OTtf>AHOiaTALLIO GOKPOUHDo Introduction The color test for reactlTe organometallic compounds has 1)6011 of xmrj great use in measuring the relati^a reaoti- Tities of sueli compomds# It has been used in GOiaparing organoiaetallio couipouMs of different metals with each other f6); for comparing the reactivity of organometallic compounds with diffarent H groups with selected reactants (7); and for distinguishing between RMgl, and Hsf% compounds (8). The color test as developed by Gilinan and Schulze (9) depended upon the formtion of tertiary alcohols by the in­ teraction of Michlsr's keton© (tetramethyl-p-diaminobenzo- pheaon©) and an organometallic coiapound, Th© test was desig­ nated as £i color test for reactive organomatallic cofflpounds, as it was thought that only th© mora reactive of these com­ pounds formed by raetals of th® first
Load more

Recommended publications
  • EI-ICHI NEGISHI Herbert C
    MAGICAL POWER OF TRANSITION METALS: PAST, PRESENT, AND FUTURE Nobel Lecture, December 8, 2010 by EI-ICHI NEGISHI Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084, U.S.A. Not long ago, the primary goal of the synthesis of complex natural products and related compounds of biological and medicinal interest was to be able to synthesize them, preferably before anyone else. While this still remains a very important goal, a number of today’s top-notch synthetic chemists must feel and even think that, given ample resources and time, they are capable of synthesizing virtually all natural products and many analogues thereof. Accepting this notion, what would then be the major goals of organic synthesis in the twenty-first century? One thing appears to be unmistakably certain. Namely, we will always need, perhaps increasingly so with time, the uniquely creative field of synthetic organic and organometallic chemistry to prepare both new and existing organic compounds for the benefit and well-being of mankind. It then seems reasonably clear that, in addition to the question of what compounds to synthesize, that of how best to synthesize them will become increasingly important. As some may have said, the primary goal would then shift from aiming to be the first to synthesize a given compound to seeking its ultimately satisfactory or “last synthesis”. If one carefully goes over various aspects of organic synthetic methodology, one would soon note how primitive and limited it had been until rather recently, or perhaps even today. For the sake of argument, we may propose here that the ultimate goal of organic synthesis is “to be able to synthesize any desired and fundamentally synthesizable organic compounds (a) in high yields, (b) efficiently (in as few steps as possible, for example), (c) selectively, preferably all in t98–99% selectivity, (d) economically, and (e) safely, abbreviated hereafter as the y(es)2 manner.” with or without catalyst R1M + R2X R1R2 + MX R1, R2: carbon groups.
    [Show full text]
  • Recent Progress in the Use of Pd-Catalyzed C-C Cross-Coupling Reactions in the Synthesis of Pharmaceutical Compounds
    http://dx.doi.org/10.5935/0103-5053.20140255 J. Braz. Chem. Soc., Vol. 25, No. 12, 2186-2214, 2014. Printed in Brazil - ©2014 Sociedade Brasileira de Química 0103 - 5053 $6.00+0.00 Review Recent Progress in the Use of Pd-Catalyzed C-C Cross-Coupling Reactions in the Synthesis of Pharmaceutical Compounds André F. P. Biajoli, Cristiane S. Schwalm, Jones Limberger, Thiago S. Claudino and Adriano L. Monteiro* Laboratory of Molecular Catalysis, Institute of Chemistry, UFRGS, Av. Bento Gonçalves, 9500, 91501-970 Porto Alegre-RS, Brazil A grande capacidade do paládio de formar ligações carbono-carbono entre substratos apropriadamente funcionalizados permitiu que os químicos orgânicos efetuassem transformações antes impossíveis ou alcançáveis somente através de rotas muito longas. Neste contexto, uma das mais elegantes e importantes aplicações das reações de acoplamento cruzado catalisadas por paládio é a síntese de compostos de interesse farmacêutico. A presente revisão tem por objetivo apresentar uma visão geral do uso de acoplamentos cruzados na síntese de componentes de medicamentos (ou de candidatos a medicamentos), independentemente da escala, compreendendo o período de 2011 até o final de julho de 2014. The impressive ability of palladium to assemble C-C bonds between appropriately functionalized substrates has allowed synthetic organic chemists to perform transformations that were previously impossible or only possible using multi-step approaches. In this context, one of the most important and elegant applications of the Pd-catalyzed C-C coupling reactions currently is the synthesis of pharmaceuticals. This review is intended to give a picture of the applications of Pd-catalyzed C-C cross-coupling reactions for the synthesis of drug components or drug candidates regardless of the scale from 2011 through to the end of July, 2014.
    [Show full text]
  • Summary of Supportive Science Regarding Thimerosal Removal
    Summary of Supportive Science Regarding Thimerosal Removal Updated December 2012 www.safeminds.org Science Summary on Mercury in Vaccines (Thimerosal Only) SafeMinds Update – December 2012 Contents ENVIRONMENTAL IMPACT ................................................................................................................................. 4 A PILOT SCALE EVALUATION OF REMOVAL OF MERCURY FROM PHARMACEUTICAL WASTEWATER USING GRANULAR ACTIVATED CARBON (CYR 2002) ................................................................................................................................................................. 4 BIODEGRADATION OF THIOMERSAL CONTAINING EFFLUENTS BY A MERCURY RESISTANT PSEUDOMONAS PUTIDA STRAIN (FORTUNATO 2005) ......................................................................................................................................................................... 4 USE OF ADSORPTION PROCESS TO REMOVE ORGANIC MERCURY THIMEROSAL FROM INDUSTRIAL PROCESS WASTEWATER (VELICU 2007)5 HUMAN & INFANT RESEARCH ............................................................................................................................ 5 IATROGENIC EXPOSURE TO MERCURY AFTER HEPATITIS B VACCINATION IN PRETERM INFANTS (STAJICH 2000) .................................. 5 MERCURY CONCENTRATIONS AND METABOLISM IN INFANTS RECEIVING VACCINES CONTAINING THIMEROSAL: A DESCRIPTIVE STUDY (PICHICHERO 2002) ......................................................................................................................................................
    [Show full text]
  • The 2010 Chemistry Nobel Prize: Pd(0)-Catalyzed Organic Synthesis
    GENERAL ARTICLE The 2010 Chemistry Nobel Prize: Pd(0)-Catalyzed Organic Synthesis Gopalpur Nagendrappa and Y C Sunil Kumar The 2010 Nobel Prize in Chemistry was awarded to three scientists, R F Heck, E-I Negishi and A Suzuki, for their work on “Palladium – Catalyzed Cross Couplings in Organic Syn- (left) G Nagendrappa thesis”. It pertains to research done over a period of four was a Professor of decades. The synthetic procedures embodied in their work Organic Chemistry at enable construction of C–C bond selectively between complex Bangalore University, molecules as in simple ones at desired positions without and Head of the Department of Medici- disturbing any functional groups at other parts of the reacting nal Chemistry, Sri molecules. The work finds wide applications in the synthesis Ramachandra (Medical) of pharmaceuticals, agricultural chemicals, and molecules for University, Chennai. electronics and other applications. It would not have been He is currently in Jain University, Bangalore. possible to synthesize some of the complex natural products or He continues to teach synthetic compounds without using these coupling reactions and do research. His in one or more steps. work is in the area of organosilicon chemis- Introduction try, synthetic and mechanistic organic In mythical stories and folk tales we come across characters that, chemistry, and clay- catalysed organic while uttering some manthras (words of charm), throw a pinch or reactions (Green fistful of a magic powder, and suddenly there appears the object Chemistry). or person they wished for or an event happens the way they want. (right) Sunil Kumar is A large number of movies have been made with such themes and a PhD from Mysore characters that would be depicted as ‘scientists’.
    [Show full text]
  • MICROREVIEW Reactivity of Polar Organometallic Compounds In
    MICROREVIEW Reactivity of Polar Organometallic Compounds in Unconventional Reaction Media: Challenges and Opportunities Joaquin García-Álvarez,*[a] Eva Hevia,*[b] and Vito Capriati*[c] This paper is gratefully dedicated to the memory of Dr. Guy Lavigne Abstract: Developing new green solvents in designing chemical chemicals in chemical transformations is, indeed, solvents used products and processes or successfully employing the already as reaction media, which account for 80–90% of mass utilization existing ones is one of the key subjects in Green Chemistry and is in a typical pharmaceutical/fine chemical operational process. especially important in Organometallic Chemistry, which is an Thus, the solvent itself is often a critical parameter especially in interdisciplinary field. Can we advantageously use unconventional drug product manufacturing and is as well responsible for most reaction media in place of current harsh organic solvents also for waste generated in the chemical industries and laboratories.[3] polar organometallic compounds? This Microreview critically Following these considerations, some of the most critical analyses the state-of-the-art on this topic and showcases recent and intriguing questions that arise are: Can we get traditional developments and breakthroughs which are becoming new research organic solvents out of organometallic reactions?[4] Can we use directions in this field. Because metals cover a vast swath of the protic, recyclable, biodegradable, and cheap unconventional periodic table, the content is organised into three Sections solvents also for highly reactive organometallic compounds? discussing the reactivity of organometallic compounds of s-, p- and Answering these questions would not only mean to break new d-block elements in unconventional solvents.
    [Show full text]
  • New Preparations and Reactions of Salt Stabilized Organozinc Reagents For
    Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München NEW PREPARATIONS AND REACTIONS OF SALT STABILIZED ORGANOZINC REAGENTS FOR THE FUNCTIONALIZATION OF AROMATICS, HETEROAROMATICS, AND ALLYLIC COMPOUNDS von Mario Ferdinand Ellwart aus München 2016 ERKLÄRUNG Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28. November 2011 von Herrn Prof. Dr. Paul Knochel betreut. EIDESSTATTLICHE VERSICHERUNG Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet. München, ………………………. ………….……………………………… (Mario F. Ellwart) Dissertation eingereicht am: 07.10.2016 1. Gutachter: Prof. Dr. Paul Knochel 2. Gutachter: Prof. Dr. Oliver Trapp Mündliche Prüfung am: 06.12.2016 This work was carried out from January 2014 to October 2016 under the guidance of Prof. Dr. Paul Knochel at the Department of Chemistry of the Ludwig-Maximilians-Universität, Munich. Firstly, I would like to express my appreciation to Prof. Dr. Paul Knochel for giving me the great opportunity to do my Ph.D. in his group and for his guidance in the course of my scientific research. I am also very grateful to Prof. Dr. Oliver Trapp for agreeing to be the second reviewer of this thesis, as well as Prof. Dr. Manfred Heuschmann, Prof. Dr. Klaus T. Wanner, Prof. Dr. Konstantin Karaghiosoff, and Prof. Dr. Regina de Vivie-Riedle for their interest shown in this manuscript by accepting to be referees. I also would like to thank Michael Eisold, Marthe Ketels, Meike Simon, and Dr. Benedikt S. Soller for the careful correction of this manuscript. I thank all past and present co-workers I have met in the Knochel group for their kindness and their help.
    [Show full text]
  • The Thimerosal Controversy
    The Thimerosal Controversy Aimee Sutherland, VRG Research Assistant April 2013 Background In the early 1920s, a major public health concern was vaccine contamination with bacteria and other germs, which could result in the death of children receiving the vaccines from tainted vials. In the book “The Hazards of Immunization”, Sir Graham S. Wilson depicts an occurrence of contamination that happened in Australia in 1928 in which twelve out of twenty-one children died after receiving the vaccine for diphtheria due to multiple staphylococcal abscesses and toxemia (FDA). This incident spurred the development of preservatives for multi-dose vials of vaccine. In 1928, Eli Lilly was the first pharmaceutical company to introduce thimerosal, an organomercury compound that is approximately 50% mercury by weight, as a preservative that would thwart microbial growth (FDA). After its introduction as a germocide, thimerosal was often challenged for its efficacy rather than its safety. The American Medical Association (AMA) published an article that questioned the effectiveness of the organomercury compounds over the inorganic mercury ones (Baker, 245). In 1938 manufacturers were required to submit safety-testing information to the Food and Drug Administration (FDA). Although preservatives had already been incorporated into many vaccines, it was not until 1968 that preservatives were required for multi-dose vials in the United States Code of Federal Regulations (FDA). In 1970s the American population, increasingly concerned about environmental contamination with heavy metals, began to have reservations about the safety of organomercury and the controversy regarding thimerosal ensued after. The Controversy In 1990s, the use of thimerosal as a preservative became controversial and was targeted as a possible cause of autism because of its mercury content.
    [Show full text]
  • Low Molecular Weight Fluorescent Probes (Lmfps) to Detect the Group 12 Metal Triad
    chemosensors Review Low Molecular Weight Fluorescent Probes (LMFPs) to Detect the Group 12 Metal Triad Ashley D. Johnson, Rose M. Curtis and Karl J. Wallace * The Department of Chemistry and Biochemistry, The University of Southern Mississippi, Hattiesburg, MS 39406, USA; [email protected] (A.D.J.); [email protected] (R.M.C.) * Correspondence: [email protected]; Tel.: +1-601-266-4715 Received: 2 March 2019; Accepted: 19 April 2019; Published: 28 April 2019 Abstract: Fluorescence sensing, of d-block elements such as Cu2+, Fe3+, Fe2+, Cd2+, Hg2+, and Zn2+ has significantly increased since the beginning of the 21st century. These particular metal ions play essential roles in biological, industrial, and environmental applications, therefore, there has been a drive to measure, detect, and remediate these metal ions. We have chosen to highlight the low molecular weight fluorescent probes (LMFPs) that undergo an optical response upon coordination with the group 12 triad (Zn2+, Cd2+, and Hg2+), as these metals have similar chemical characteristics but behave differently in the environment. Keywords: chemosensors; fluorescence; recognition; sensing; group 12 metals (zinc; cadmium; and mercury) 1. Introduction Sensors are used in every aspect of modern life; for example, many modern households have a carbon monoxide sensor or a smoke detector installed. In industry, fiber-optic sensors are used for monitoring process variables, such as temperature, pressure flow, and the level of a liquid. The environment requires sensors to monitor toxic gases and air pollution, and in clinical applications for the detection of medical conditions, i.e., Type 1 diabetes. The field of sensor technology has rapidly been expanding over the last several decades, and the field can be categorized into two broad areas (1) chemical sensors and (2) biosensors.
    [Show full text]
  • Ep 0398147 B1
    Europa,schesP_ MM M II II INI Ml M I M IN II I II J European Patent Office © Publication number: 0 398 147 B1 Office_„. europeen des brevets © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 09.11.94 © Int. CI.5: C08J 9/14, //(C08J9/14, C08L75:04) © Application number: 90108748.6 @ Date of filing: 09.05.90 © A foaming system for rigid urethane and Isoyanurate foams. ® Priority: 10.05.89 US 350184 © Proprietor: THE DOW CHEMICAL COMPANY (a Delaware corporation) @ Date of publication of application: 2030 Dow Center 22.11.90 Bulletin 90/47 Abbott Road Midland Michigan 48640 (US) © Publication of the grant of the patent: 09.11.94 Bulletin 94/45 @ Inventor: Smlts, Guldo Freddy Veldstraat 37 © Designated Contracting States: B-2110 Wljnegem (BE) AT BE CH DE DK ES FR GB GR IT LI LU NL SE Inventor: Grunbauer, Henri Jacobus Marie Schorploen 45 © References cited: NL-4501 HC Oostburg (BE) EP-A- 0 330 988 US-A- 3 583 921 US-A- 4 624 970 © Representative: Huber, Bernhard, Dlpl.-Chem. et al Patentanwalte H. Welckmann, Dr. K. Flncke F.A. Welckmann, B. Huber Dr. H. Llska, Dr. J. Prechtel, Dr. B. Bohm Postfach 86 08 20 uD-81635 \J i \J\J\J iviuMunchen ■ ■ vs ■ ■ v> ■ ■ (DE) QQ. yi^i— j 00 Oi oo Note: Within nine months from the publication of the mention of the grant of the European patent, any person ® may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition Q,.
    [Show full text]
  • The Synthesis of Molecular Switches
    ! ! " ! # $% & ' ()) *&& +,-+./(-, *& /0./+.0-10-.--.) % 23 33 ' 4 5' &6 Abstract According to the famous axiom known as Moore’s Law the number of transistors that can be etched on a given piece of silicon, and therefore the computing power, will double every 18 to 24 months. For the last 40 years Moore’s prediction has held true as computers have grown more and more powerful. However, around 2020 hardware manufac- turers will have reached the physical limits of silicon. A proposed so- lution to this dilemma is molecular electronics. Within this field re- searchers are attempting to develop individual organic molecules and metal complexes that can act as molecular equivalents of electronic components such as diodes, transistors and capacitors. By utilizing molecular electronics to construct the next generation of computers processors with 100,000 times as many components on the same sur- face area could potentially be created. We have synthesized a range of new pyridyl thienopyridine ligands and compared the electrochemical and photophysical properties of their corresponding Ru(II) complexes with that with the Ru(II) com- plexes of a variety of ligands based on 6-thiophen-2-yl-2,2´-bipyridine and 4-thiophen-2-yl-2,2´-bipyridine. While the electrochemistry of the 2+ Ru(II) complexes were similar to that of unsubstituted [Ru(bpy)3] , substantial differences in luminescence lifetimes were found. Our findings show that, due to steric interactions with the auxiliary bipy- ridyl ligands, luminescence is quenched in Ru(II) complexes that in- corporate the 6-thiophen-2-yl-2,2´-bipyridine motif, while it is on par 2+ with the luminescence of [Ru(bpy)3] in the Ru(II) complexes of the pyridyl thienopyridine ligands.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,933,353 B2 Wan 45) Date of Patent: Aug
    USOO6933353B2 (12) United States Patent (10) Patent No.: US 6,933,353 B2 Wan 45) Date of Patent: Aug. 23,9 2005 (54) OLEFIN POLYMERIZATION PROCESS 6,489,408 B2 12/2002 Mawson et al. .............. 526/68 6,524.986 B2 2/2003 Costa et al. .......... ... 502/109 (75) Inventor: Shaotian Wang, Mason, OH (US) 6,541,583 B2 4/2003 Meverden et al. .......... 526/127 6,559,251 B1 * 5/2003 Wang et al. .......... ... 526/127 (73) Assignee: Equistar Chemicals, LP, Houston, TX 6,765,074 B2 7/2004 Sartain ....................... 526/153 (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO O1/53360 5/1999 patent is extended or adjusted under 35 WO WO 99/24446 7/2001 U.S.C. 154(b) by 92 days. OTHER PUBLICATIONS (21) Appl. No.: 10/614,615 Soga et al., Macromolecules 27 (1994) 7938–7940. Buu-Hoi and Xuong, J. Chem. Soc. (1952) 2225. (22) Filed: Jul. 7, 2003 Jingling et al., J. Organometal. Chem. 460 (1993) 191. (65) Prior Publication Data Noh, et al., J. Organometal. Chem, 518 (1996) 1. Noh, et al., J. Organometal. Chem, 580 (1999) 90. US 2005/0010004 A1 Jan. 13, 2005 * cited by examiner (51) Int. Cl. ............................... C08F 4/44; CO8F 4/52 (52) U.S. Cl. ....................... 526/114; 526/116; 526/161; Primary Examiner-David W. Wu 526/172; 526/148; 526/151; 526/130; 526/129; ASSistant Examiner-Rip A. Lee 526/348.5; 526/348.4; 526/348.6; 526/351; (74) Attorney, Agent, or Firm- John Tyrell; Jonathan L.
    [Show full text]
  • Signature of Author
    NEW METHODS FOR THE FORMATION OF CARBON-CARBON BONDS VIA ORGANOMETALLIC COMPOUNDS by BRIAN SCOTT BRONK B.A. (High Honors), Colgate University (1989) SUBMITTED TO THE DEPARTMENT OF CHEMISTRY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY February 1995 © Massachusetts Institute of Technology, 1995 Signature of Author.. ........................................................... Department of Chemistry September 19, 1994 /' I . N 'N Certified by....................... ......... .. ........................................ Certifiedby Rick L. Danheiser Thesis Supervisor Certified by ......... ... ...................................... Stephen J. Lippard A Thesis Supervisor // . Accepted by.................. .................... /../.!.............................................. Dietmar Seyferth Departmental Committee on Graduate Studies I:;. .i., . : .1'_I_ , This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: n An Professor Stephen L. Buchw ald ....... ............................. m L. BcChairman Professor Rick L. Danheiser . ................... Thesis Supervisor Professor Stephen J. Lippard ........... ........ .................... Thesis Supervisor Professor Dietmar Seyferth ............ .......... -.... 2 ACKNOWLEDGMENTS After writing a thesis totaling over 300 pages, the task of writing one final page would seem quite simple. Unfortunately, I am left with a single page to express my gratitude to :l who have made
    [Show full text]