A Dissertation Entitled the Study of Lanthanides for Organometallic And
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
1 Introduction to Early Main Group Organometallic Chemistry and Catalysis
1 1 Introduction to Early Main Group Organometallic Chemistry and Catalysis Sjoerd Harder University Erlangen-Nürnberg, Inorganic and Organometallic Chemistry, Egerlandstrasse 1, 91058 Erlangen, Germany 1.1 Introduction Although organometallic complexes of the early main groups are well known for their very high reactivity and challenging isolation, they are among the first stud- ied during the pioneering beginnings of the field. Their high nucleophilicity and Brønsted basicity have made them to what they are today: strong polar reagents that are indispensible in modern organic synthesis. It is exactly this high reactivity that has made them potent catalysts for organic transformations that are gener- ally catalyzed by transition metal complexes. Despite their lack of partially filled d-orbitals and their inability to switch reversibly between oxidation states, the scope of their application in catalysis is astounding. As the early main group metal catalysis only started to become popular since the beginning of this century, it is still a young field with ample opportunities for further development. This intro- ductory chapter is specifically written for new graduate students in the field. It gives a very compact overview of the history of early main group organometallic chemistry, synthetic methods, bonding and structures, analytical methods, solu- tion dynamics, and some preliminary low-valent chemistry. This forms the basis for understanding their use in catalysis for which the basic steps are described in the second part of this chapter. For further in-depth information, the reader is referred to the individual chapters in this book. 1.2 s-Block Organometallics 1.2.1 Short History The organometallic chemistry of the highly electropositive early main group metals could not have started without the isolation of these elements in the metallic state. -
1 Introduction
1 Field-control, phase-transitions, and life’s emergence 2 3 4 Gargi Mitra-Delmotte 1* and A.N. Mitra 2* 5 6 7 139 Cite de l’Ocean, Montgaillard, St.Denis 97400, REUNION. 8 e.mail : [email protected] 9 10 2Emeritius Professor, Department of Physics, Delhi University, INDIA; 244 Tagore Park, 11 Delhi 110009, INDIA; 12 e.mail : [email protected] 13 14 15 16 17 18 19 *Correspondence: 20 Gargi Mitra-Delmotte 1 21 e.mail : [email protected] 22 23 A.N. Mitra 2 24 e.mail : [email protected] 25 26 27 28 29 30 31 32 33 34 35 Number of words: ~11748 (without Abstract, references, tables, and figure legends) 36 7 figures (plus two figures in supplementary information files). 37 38 39 40 41 42 43 44 45 46 47 Abstract 48 49 Critical-like characteristics in open living systems at each organizational level (from bio- 50 molecules to ecosystems) indicate that non-equilibrium phase-transitions into absorbing 51 states lead to self-organized states comprising autonomous components. Also Langton’s 52 hypothesis of the spontaneous emergence of computation in the vicinity of a critical 53 phase-transition, points to the importance of conservative redistribution rules, threshold, 54 meta-stability, and so on. But extrapolating these features to the origins of life, brings up 55 a paradox: how could simple organics-- lacking the ‘soft matter’ response properties of 56 today’s complex bio-molecules--have dissipated energy from primordial reactions 57 (eventually reducing CO 2) in a controlled manner for their ‘ordering’? Nevertheless, a 58 causal link of life’s macroscopic irreversible dynamics to the microscopic reversible laws 59 of statistical mechanics is indicated via the ‘functional-takeover’ of a soft magnetic 60 scaffold by organics (c.f. -
Page 1 of 13 Pleasersc Do Not Advances Adjust Margins
RSC Advances This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. This Accepted Manuscript will be replaced by the edited, formatted and paginated article as soon as this is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/advances Page 1 of 13 PleaseRSC do not Advances adjust margins RSC Advances REVIEW Applications of supramolecular capsules derived from resorcin[4]arenes, calix[n]arenes and metallo-ligands: from Received 00th January 20xx, Accepted 00th January 20xx biology to catalysis a a,b a DOI: 10.1039/x0xx00000x Chiara M. A. Gangemi, Andrea Pappalardo* and Giuseppe Trusso Sfrazzetto* www.rsc.org/ Supramolecular architectures developed after the initial studies of Cram, Lehn and Pedersen have become structurally complexes but fascinating. In this context, supramolecular capsules based on resorcin[4]arenes, calix[n]arenes or metal- ligand structures are dynamic assemblies inspired to biological systems. -
Organometallic Catalysts in Synthetic Organic Chemistry: from Reactions in Aqueous Media to Gold Catalysis*
Pure Appl. Chem., Vol. 80, No. 5, pp. 831–844, 2008. doi:10.1351/pac200880050831 © 2008 IUPAC Organometallic catalysts in synthetic organic chemistry: From reactions in aqueous media to gold catalysis* Jean-Pierre Genêt‡, Sylvain Darses, and Véronique Michelet Selective Organic Synthesis and Natural Products Laboratory, Ecole Nationale Supérieure de Chimie de Paris, UMR CNRS 7573, 11 rue P. et M. Curie, 75231 Paris Cedex 05, France Abstract: Water has attracted significant attention as an alternative solvent for transition- metal-catalyzed reactions. The use of water as solvent allows simplified procedures for sep- aration of the catalyst from the products and recycling of the catalyst. Water is an inexpen- sive reagent for the formation of oxygen-containing products such as alcohols. The use of water as a medium for promoting organometallic and organic reactions is also of great po- tential. This chapter will focus on old and recent developments in the design and applications of some catalytic reactions using aqueous-phase Pd, Rh, Pt, and Au complexes. Keywords: water; catalysis; palladium; gold; rhodium; potassium organotrifluoroborates; asymmetric 1,4-addition; recycling. INTRODUCTION Over the past few years, significant research has been directed toward the development of new tech- nologies for environmentally benign processes. The use of water as solvent in homogeneous metal-cat- alyzed reactions has gained increasing attention because of the potential environmental and economic benefits of replacing organic solvents with water. Indeed, water is an attractive solvent because it is in- expensive and nontoxic; the most attractive feature is its utility in the development of green and envi- ronmentally safe processes [1]. -
Comprehensive Organometallic Chemistry II a Review of the Literature 1982-1994
Comprehensive Organometallic Chemistry II A Review of the Literature 1982-1994 Editors-in-Chief Edward W. Abel University ofExeter, UK F. Gordon A. Stone Baylor University, Waco, TX, USA Geoffrey Wilkinson Imperial College of Science, Technology and Medicine, London, UK Volume 1 LITHIUM, BERYLLIUM, AND BORON GROUPS Volume Editor Catherine E. Housecroft Institut für Anorganische Chemie der Universität Basel, Switzerland PERGAMON Contents of All Volumes Volume 1 Lithium, Beryllium, and Boron Groups 1 Alkali Metals 2 Beryllium 3 Magnesium, Calcium, Strontium and Barium 4 Compounds with Three- or Four-coordinate Boron, Emphasizing Cyclic Systems 5 Boron Rings Ligated to Metals 6 Polyhedral Carbaboranes 7 Main-group Heteroboranes 8 Metallaboranes 9 Transition Metal Metallacarbaboranes 10 Aluminum 11 Gallium, Indium and Thallium, Excluding Transition Metal Derivatives 12 Transition Metal Complexes of Aluminum, Gallium, Indium and Thallium Author Index Subject Index Volume 2 Silicon Group, Arsenic, Antimony, and Bismuth 1 Organosilanes 2 Carbacyclic Silanes 3 Organopolysilanes 4 Silicones 5 Germanium 6 Tin 7 Lead 8 Arsenic, Antimony and Bismuth Author Index Subject Index Volume 3 Copper and Zinc Groups 1 Gold 2 Copper and Silver 3 Mercury 4 Cadmium and Zinc Author Index Subject Index Volume 4 Scandium, Yttrium, Lanthanides and Actinides, and Titanium Group 1 Zero Oxidation State Complexes of Scandium, Yttrium and the Lanthanide Elements 2 Scandium, Yttrium, and the Lanthanide and Actinide Elements, Excluding their Zero Oxidation State Complexes -
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) ...................................................................................................................................................... -
Organometallic Chemistry BASIC PRINCIPLES, APPLICATIONS, and a FEW CASE STUDIES
Safety Moment TYLER LAB GROUP MEETING 1 Safety Moment TYLER LAB GROUP MEETING 2 Metal Hydrides: Benchtop vs. Box Hydride = :H- Hydrides are powerful Lewis bases and reducing agent ◦ Exothermically form H2 (this should scare you) ◦ Heating leads to faster reactivity ◦ H evolution leads to rapid increase in pressure2 ◦ Uncontrolled reactions easily cause runaway exotherm, class D fire, explosion, and death/unemployment LiAlH is the #1 chemical cause of fatality in chemical4 industry 3 Metal Hydrides: “I want to commit the murder I was imprisoned for†.” LiAlH4 ◦ Insanely irritating (serious safety hazard) ◦ Extremely moisture sensitive (don’t leave out for >2 minutes) ◦ Ethereal mixtures are pyrophoric! DiBuAl-H ◦ Pyrophoric – it will explode upon exposure to oxygen NaEt3BH ◦ Pyrophoric in solution LiH and NaH ◦ Can be handled on the benchtop (not >2 minutes) ◦ Parrafin oil dispersions much safer KH ◦ Pyrophoric if not in a dispersion ◦ Handle with extreme care! † Sirius Black, Harry Potter and the Prisoner of Azkaban 4 Metal Hydrides: “I want to commit the murder I was imprisoned for†.” CaH2 ◦ Very safe to handle on the benchtop Pt-H, Pd-H, Ni-H ◦ All very pyrophoric NaBH4 ◦ Very safe in general Other hydrides ◦ Treat as pyrophoric ◦ Transition metal hydrides vary in hydridic strength ◦ General rule of thumb: if it does hydrogenations, it is probably pyrophoric ◦ If they’re in organics of any kind, they are probably pyrophoric † Sirius Black, Harry Potter and the Prisoner of Azkaban 5 Organometallic Chemistry BASIC PRINCIPLES, APPLICATIONS, -
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. -
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. -
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,. -
Dalton Transactions Accepted Manuscript
Dalton Transactions Accepted Manuscript This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the Information for Authors. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s standard Terms & Conditions and the Ethical guidelines still apply. In no event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. www.rsc.org/dalton Page 1 of 13 PleaseDalton do not Transactions adjust margins Dalton Transactions PERSPECTIVE Rare-Earth Metal πππ-Complexes of Reduced Arenes, Alkenes, and Alkynes: Bonding, Electronic Structure, and Comparison with Received 00th January 20xx, Accepted 00th January 20xx Actinides and Other Electropositive Metals a,b a,c DOI: 10.1039/x0xx00000x Wenliang Huang, and Paula L. Diaconescu www.rsc.org/ Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. -
20 Catalysis and Organometallic Chemistry of Monometallic Species
20 Catalysis and organometallic chemistry of monometallic species Richard E. Douthwaite Department of Chemistry, University of York, Heslington, York, UK YO10 5DD Organometallic chemistry reported in 2003 again demonstrated the breadth of interest and application of this core chemical field. Significant discoveries and developments were reported particularly in the application and understanding of organometallic compounds in catalysis. Highlights include the continued develop- ment of catalytic reactions incorporating C–H activation processes, the demonstra- 1 tion of inverted electronic dependence in ligand substitution of palladium(0), and the synthesis of the first early-transition metal perfluoroalkyl complexes.2 1 Introduction A number of relevant reviews and collections of research papers spanning the transition metal series were published in 2003. The 50th anniversary of Ziegler catalysis was commemorated3,4 and a survey of metal mediated polymerisation using non-metallocene catalysts surveyed.5 Journal issues dedicated to selected topics included metal–carbon multiple bonds and related organometallics,6 developments in the reactivity of metal allyl and alkyl complexes,7 metal alkynyls,8 and carbon rich organometallic compounds including 1.9 Reviews of catalytic reactions using well-defined precatalyst complexes include alkene ring-closing and opening methathesis using molybdenum and tungsten imido DOI: 10.1039/b311797a Annu. Rep. Prog. Chem., Sect. A, 2004, 100, 385–406 385 alkylidene precatalysts,10 chiral organometallic half-sandwich