Organometallic Chemistry Is Described to Better Acquaint the Reader with the Field
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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. -
Modern-Reduction-Methods.Pdf
Modern Reduction Methods Edited by Pher G. Andersson and Ian J. Munslow Related Titles Yamamoto, H., Ishihara, K. (eds.) Torii, S. Acid Catalysis in Modern Electroorganic Reduction Organic Synthesis Synthesis 2008 2006 ISBN: 978-3-527-31724-0 ISBN: 978-3-527-31539-0 Roberts, S. M. de Meijere, A., Diederich, F. (eds.) Catalysts for Fine Chemical Metal-Catalyzed Cross- Synthesis V 5 – Regio and Coupling Reactions Stereo-Controlled Oxidations 2004 and Reductions ISBN: 978-3-527-30518-6 2007 Online Book Wiley Interscience Bäckvall, J.-E. (ed.) ISBN: 978-0-470-09024-4 Modern Oxidation Methods 2004 de Vries, J. G., Elsevier, C. J. (eds.) ISBN: 978-3-527-30642-8 The Handbook of Homogeneous Hydrogenation 2007 ISBN: 978-3-527-31161-3 Modern Reduction Methods Edited by Pher G. Andersson and Ian J. Munslow The Editors All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Pher G. Andersson publisher do not warrant the information Uppsala University contained in these books, including this book, to Department of Organic Chemistry be free of errors. Readers are advised to keep in Husargatan 3 mind that statements, data, illustrations, 751 23 Uppsala procedural details or other items may Sweden inadvertently be inaccurate. Dr. Ian J. Munslow Library of Congress Card No.: Uppsala University applied for Department of Biochemistry and Organic Chemistry Husargatan 3 British Library Cataloguing-in-Publication Data 751 23 Uppsala A catalogue record for this book is available from Sweden the British Library. Bibliographic information published by the Deutsche Nationalbibliothek Die Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>. -
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]. -
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Volume 10, Issue 3, 2020, 5412 - 5417 ISSN 2069-5837 Biointerface Research in Applied Chemistry www.BiointerfaceResearch.com https://doi.org/10.33263/BRIAC103.412417 Original Research Article Open Access Journal Received: 26.01.2020 / Revised: 02.03.2020 / Accepted: 03.03.2020 / Published on-line: 09.03.2020 Obtaining salts of resin acids from Cuban pine by metathesis reactions Olinka Tiomno-Tiomnova 1 , Jorge Enrique Rodriguez-Chanfrau 2 , Daylin Gamiotea-Turro 2 , Thayná Souza Silva 3 , Carlos Henrique Gomes Martins 3 , Alexander Valerino-Diaz 2 , Yaymarilis Veranes-Pantoja 4 , Angel Seijo-Santos 1 , Antonio Carlos Guastaldi 2 1Center of Engineering and Chemical Investigations. Havana. CP 10600, Cuba 2Group of Biomaterials, Department of Physical Chemistry, Institute of Chemistry, Sao ~ Paulo State University (UNESP), Araraquara, SP, 14800-060, Brazil 3Laboratory of Research on Antimicrobial Trials (LaPEA), Institute of Biomedical Sciences – ICBIM, Federal University of Uberlândia, Uberlândia, Brazil 4Biomaterials Center. University of Havana. Havana. CP 10600, Cuba *corresponding author e-mail address: [email protected] | Scopus ID 7801488065 ABSTRACT The resin acids obtained from the Cuban pine rosin are the starting material for the development and application of metathesis reactions. These reactions allow the obtaining of salts with high added value which could be used in the development of biomaterials for dental use. The objective of this work was to obtain calcium, magnesium and zinc resinates from the resin acid obtained from the Cuban pine resin by metathesis reaction for possible use in the development of biomaterials. The products obtained were evaluated by elemental analysis, X-ray powder diffraction, infrared spectroscopy, scanning electron microscopy associated with electron dispersion spectroscopy, nuclear magnetic resonance and biological tests (antibacterial activity). -
A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates
Portland State University PDXScholar Dissertations and Theses Dissertations and Theses Winter 4-3-2015 A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates Kuruppu Lilanthi Jayatissa Portland State University Follow this and additional works at: https://pdxscholar.library.pdx.edu/open_access_etds Part of the Catalysis and Reaction Engineering Commons Let us know how access to this document benefits ou.y Recommended Citation Jayatissa, Kuruppu Lilanthi, "A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates" (2015). Dissertations and Theses. Paper 2229. https://doi.org/10.15760/etd.2226 This Thesis is brought to you for free and open access. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of PDXScholar. Please contact us if we can make this document more accessible: [email protected]. A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates. by Kuruppu Lilanthi Jayatissa A thesis submitted in partial fulfillment of the requirement for the degree of Master of Science in Chemistry Thesis Committee: David Stuart, Chair Robert Strongin Theresa McCormick Portland State University 2015 Abstract Biaryl moieties are important structural motifs in many industries, including pharmaceutical, agrochemical, energy and technology. The development of novel and efficient methods to synthesize these carbon-carbon bonds is at the forefront of synthetic methodology. Since Ullmann’s first report of stoichiometric Cu-mediated homo-coupling of aryl halides, there has been a dramatic evolution in transition metal catalyzed biaryl cross-coupling reactions. -
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 -
MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS and EVALUATION in ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008
UNIVERSITAT ROVIRA I VIRGILI MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008 PhD Thesis MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa Tarragona, July 2008 UNIVERSITAT ROVIRA I VIRGILI MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008 UNIVERSITAT ROVIRA I VIRGILI MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008 Institut Catalá d’Investigació Química Memoria presentada por Dana Madeleine Popa para optar al título de Doctor por la Universitat Rovira i Virgili. Revisada por Dr. Anton Vidal Dr. Miquel A. Pericàs UNIVERSITAT ROVIRA I VIRGILI MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008 UNIVERSITAT ROVIRA I VIRGILI MODULAR PHOSPHINOOXAZOLINES: SYNTHESIS AND EVALUATION IN ALLYLIC SUBSTITUTIONS Dana Madeleine Popa ISBN:978-84-691-8862-0/DL:T-1275-2008 El presente trabajo de investigación ha sido realizado en el Institut Català d`Investigació Química, bajo la dirección de Dr. Anton Vidal y al Dr. Miquel A. Pericàs, a quienes les quiero dar las gracias por la oportunidad que me han ofrecido de formarme como investigadora bajo su supervisión. Quiero agradecer a Dr. Anton Vidal por los consejos y ayuda que me ha ofrecido día a día. Agradezco a Dr. Miquel A. Pericàs por el soporte que me ha proporcionado en todo el momento. Quiero agradecer también a Sergi Rodríguez Escrich por su colaboración en una parte del trabajo de investigación realizado. -
N-Heterocyclic Carbene Ligands for Iridium- Catalysed Asymmetric Hydrogenation
N-Heterocyclic Carbene Ligands for Iridium- Catalysed Asymmetric Hydrogenation Inauguraldissertation zur Erlangung der Würde eines Doktors der Philosophie vorgelegt der Philosophisch-Naturwissenschaftlichen Fakultät der Universität Basel von Steve Nanchen aus Lens / Schweiz Basel 2005 Genehmigt von der Philosophisch-Naturwissenschaftlichen Fakultät auf Antrag von: Prof. Dr. Andreas Pfaltz Prof. Dr. Wolf-Dietrich Woggon Basel, den 20. September 2005 Prof. Dr. Hans-Jakob Wirz Dekan to my wife Annik Acknowledgments I thank Professor Andreas Pfaltz to have given me the opportunity of joining his group, for his help and constant support over the last four years. I also thank Professor Wolf-Dietrich Woggon who agreed to co-examine this thesis. Dr. Valentin Köhler, Dr. William Drury III, Dr. Geoffroy Guillemot and Dr. Benoît Pugin, Solvias AG, are acknowledged for helpful discussions and fruitful collaboration. I am grateful to Markus Neuburger and Dr. Silvia Schaffner for recording numerous X-ray data and for refining X-ray structures. Dr. Klaus Kulicke, Axel Franzke and Dr. Clément Mazet are acknowledged for their countless hours recording 2D NMR spectra and their help on interpretation of data. I thank Björn Gschwend, Dominik Frank and Peter Sommer for their laboratory work contributions. Thanks to Dr. Cara Humphrey, Dr. Geoffroy Guillemot and Dr. Yann Ribourdouille for proof-reading the manuscript. A special thanks goes to the members of the Pfaltz group who have made my stay in Basel an enjoyable time. Thanks to lab 204 for the nice working atmosphere. A big thanks to my friends and family. Their help and presence during these four years was invaluable. Finally, thanks to Annik for all her support and love. -
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, -
THAT ARE NOT ALLOLLIKULTTUUS009958363B2 (12 ) United States Patent ( 10 ) Patent No
THAT ARE NOT ALLOLLIKULTTUUS009958363B2 (12 ) United States Patent ( 10 ) Patent No. : US 9 , 958 ,363 B2 Smart et al. (45 ) Date of Patent: May 1 , 2018 ( 54 ) FLUOROUS AFFINITY EXTRACTION FOR (56 ) References Cited IONIC LIQUID - BASED SAMPLE PREPARATION U . S . PATENT DOCUMENTS 7 ,273 ,587 B1 9 / 2007 Birkner et al . ( 71 ) Applicant: Agilent Technologies , Inc. , Loveland , 7 ,273 ,720 B1 9 / 2007 Birkner et al. CA (US ) ( Continued ) ( 72 ) Inventors: Brian Phillip Smart, San Jose , CA (US ) ; Brooks Bond - Watts , Fremont, FOREIGN PATENT DOCUMENTS CA (US ) ; James Alexander Apffel, Jr ., WO WO2007110637 10 /2007 Mountain View , CA (US ) WO WO2011155829 12 / 2011 ( 73 ) Assignee : Agilent Technologies , Inc ., Santa Clara , OTHER PUBLICATIONS CA (US ) Yuesheng Ye , Yossef A . Elabd “ Anion exchanged polymerized ionic ( * ) Notice : Subject to any disclaimer, the term of this liquids: High free volume single ion conductors ” Polymer 52 ( 2011 ) patent is extended or adjusted under 35 1309 - 1317 , plus supplementary data ( pp . 1 - 6 ) . * U . S . C . 154 (b ) by 168 days . (Continued ) ( 21) Appl . No. : 14 /724 ,656 Primary Examiner — Christine T Mui ão( 22 ) Filed : May 28 , 2015 Assistant Examiner - Emily R . Berkeley (6565 ) Prior Publication Data (57 ) ABSTRACT US 2015 /0369711 A1 Dec . 24 , 2015 A method for removing an ionic liquid from an aqueous Related U . S . Application Data sample is provided . In some embodiments , the method includes : ( a ) combining an aqueous sample including an ( 60 ) Provisional application No . 62/ 016 ,000 , filed on Jun . ionic liquid with an ion exchanger composition including an 23 , 2014 , provisional application No . 62 /016 , 003 , ion exchanger counterion to produce a solution including a (Continued ) fluorous salt of the ionic liquid , where at least one of the ionic liquid and the ion exchanger counterion is fluorinated ; (51 ) Int .