DOCSLIB.ORG

The Photochemical Dimerization of Norbornadiene Using Chromium

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

The photochemical dimerization of norbornadiene using chromium carbonyls by Brian Kellog Hill A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in Chemistry Montana State University © Copyright by Brian Kellog Hill (1969) Abstract: Norbornadiene has previously been shown to undergo dimerization photochemically with Group VI and VIII and thermally with Group VIII unsubstituted metal carbonyls. Furthermore, diene-iron-tricarbonyls cause the reaction to be more stereospecific and give only two products instead of the usual eleven obtained using the unsubstituted metal carbonyls. To learn if this change in products was generally characteristic of unsubstituted and substituted metal carbonyls a series of chromium carbonyls were investigated. The products of the chromium metal carbonyls were three trans dimers, a saturated cage dimer and one ketone insertion product. A possible mechanism for the photochemical dimerization of norbornadiene using chromium hexacarbonyl and substituted chromium carbonyl as sensitizers was determined. A common intermediate for the reactions has been proposed. THE PHOTOCHEMICAL DIMERIZATION OF NORBORNADIENE USING CHROMIUM CARBONYLS' by BRIAN KELLOGG HILL A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in , C h em istry Approved: Head, Major Department CHairmanT ExaumhingC om m ittee MONTANA STATE UNIVERSITY Bozeman,' Montana August, 1969 ill ACKNOWLEDGEMENT The author would like to acknowledge Dr..E. W. Jennings for his encouragement and advice, without which this research would not have been completed. Special recognition is due the author's wife, Gayle, for her confi­ dence and sacrifices. Appreciation is expressed to the National Defense Education Act for the financial assistance of a fellowship. iv TABLE OF CONTENTS Page LIST OF TABLES .....................................i . ■....................................... ......................... v i LIST OF FIGURES .......................................................................................................... v ii ABSTRACT ..... ................................................................................' ........................ x IN T R O D U C T IO N ............................................................................................................. I D IS C U S S IO N ................................................................................................ '.................. 25 Procedure for Determining Products and Product R atios ....................................................................................................................... 27 Isolation of Intermediates Using Chromium Hexacarbonyl ............. ■......................................... ■................................................ 34 Isolation of Intermediates for Benzene, Toluene or M e sity le n e Chromium T ric a rb o n y l............................................................... 41 O th er I n v e s t i g a t i o n s ......................................................................................... 56 CONCLUSION ................................................................................................................. 60 EXPERIMENTAL..............................................' .....................' ........................................ 70 R e a g e n ts .................................................................................................................... 70 Instruments ........................................................... 71 Light and Reaction Systems ............................................................................ 72 Photoreaction for Determining Products and Product R atios ............................................................................................................. ... 73 Isolation of Photoreaction Intermediates ................................. .... 81 Photochemical Time Study ............................................................................... 85 B eer's L a w ................................................................................ 86 In frared S t u d y ....................................................................................................... 86 Thermal Reaction of Chromium Hexacarbonyl and Norbornadiene .................................................... 86 Irradiation of Norbornadiene Without Metal C arbonyl ...........................87 P h o to re a c tio n of N o rb o rn e n e ..................................................... 87 V Page EXPERIMENTAL (continued) Thermal Reaction of Pyridine Chromium Pentacarbonyl and Norbornadiene ......................................................................................... 87 Thermal Reaction of Dipyridine Chromium Tetracarbonyl and Norbornadiene ........................................................ 88 Isolation of Carbonyl Polym er .................................................................. 89, LITERATURE CITED 90 v i LIST OF TABLES Page I. Transition Complexes With Norbornadiene ........................................ 14 II. Dimers, Trimers and Ketones of Norbornadiene .............................. 15 III. Metal Carbonyl Reactant Templates . ........................................... 25 IV. Experimental Procedure for Product Identification ........................... 2 8 V. P roduct R atios o f N orbornadiene D im e rs ............................................... 32 VI. Peak Assignments for the Mass Spectrum of the Red C om plex ................................................................................................................. 50 v ii LIST OF FIGURES Page 1. Pictorial Representation of the Bond Between Platinum and Ethylene ..................................................... .......................... 4 2. Pictorial Representation of a Metal Carbonyl Bond ....................... 7 3. S tru ctu re o f a Bridged and T riple Bridged C a r b o n y l........................ 8 4. Non-concerted Mechanism for the Formation of N o rb o rn ad ien e D i m e r s ............................................... 23 5. Nuclear Magnetic Resonance Spectra of N o rb o rn ad ien e D i m e r s ................................................................................... 29 6. Nuclear Magnetic Resonance Spectrum of N o rb o rn ad ien e C age D i m e r ......................................................................... 30 7. Infrared Spectrum of Chromium Hexacarbonyl Solution at Zero. Time of Irradiation ................................. ... 36 8 . Infrared Spectrum of Chromium Hexacarbonyl Solution after Two Hours of Irradiation . .............................. ... 3 6 9. Infrared Spectrum of Chromium Hexacarbonyl S o lu tio n a fte r Six H ours of I r r a d i a t i o n .................................................... 37 10. Infrared Spectrum of Chromium Hexacarbonyl Solution after Two Hours of Irradiation and Six H ours in th e D a r k ................................................................................'. ■ 39 IT. Infrared Spectrum of Mesitylene Chromium T ricarbonyl S olution a t Zero Time o f I r r a d i a tio n .............................. 43 12. Infrared Spectrum of Mesitylene Chromium Tricarbonyl Solution after 30 Minutes of Irradiation .................... 43 13. Infrared Spectrum of Mesitylene Chromium Tricarbonyl Solution after One Hour of Irradiation ....................... 44 14. Infrared Spectrum of Mesitylene Chromium Tricarbonyl Solution after 3^/2 Hours of Irradiation ....................... 44 15. Infrared Spectrum of Mesitylene Chromium Tricarbonyl Solution after 30 Minutes of Irradiation and Six Hours in the Dark .............................. ............................................. 45 v iii P age 16. Mass Spectrum of Norbornadiene Chromium T e tra c a rb o n y l...................................................................................... ' ............... 47 17. In frared Spectrum o f Red C o m p le x ........................... ................................ 48 18. M ass Spectrum o f Red C o m p le x ........................... ................ ................... 49 19. Infrared Spectrum of Benzene Chromium Tricarbonyl a t Zero Time of I r r a d i a t i o n ......................................................................... 52 20. Infrared Spectrum of Benzene Chromium Tricarbonyl a fte r 30 M in u tes o f I r r a d ia tio n .................................................. ............... 52 21. Infrared Spectrum of Benzene Chromium Tricarbonyl after One Hour of Irradiation ..................................................................... 53 22. Infrared Spectrum of Benzene Chromium Tricarbonyl a fte r 31/2 H ours o f Irra d ia tio n .................................................................. 53 . 23. Infrared Spectrum of Toluene Chromium Tricarbonyl a t Zero Time of I r r a d i a t i o n ......................................................................... 54 24. Infrared Spectrum of Toluene Chromium Tricarbonyl a fte r 30 M in u tes o f I r r a d ia tio n ..................................... .............................. 54 25. Infrared Spectrum of Toluene Chromium Tricarbonyl a fte r O ne H our of I r r a d i a tio n ...................................................................... 55 26. Infrared Spectrum of Toluene Chromium Tricabonyl a fte r 3Yz Hours of Irradiation .................................................................
Recommended publications
  • Arenechromium Tricarbonyl Complexes: Conformational

    Arenechromium Tricarbonyl Complexes: Conformational

    η6 – ARENECHROMIUM TRICARBONYL COMPLEXES: CONFORMATIONAL ANALYSIS, STEREOCONTROL IN NUCLEOPHILIC ADDITION AND APPLICATIONS IN ORGANIC SYNTHESIS by HARINANDINI PARAMAHAMSAN Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Thesis Advisor: Prof. Anthony J. Pearson Department of Chemistry CASE WESTERN RESERVE UNIVERSITY May 2005 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the dissertation of Harinandini Paramahamsan candidate for the Ph.D. degree*. (signed) Prof. Philip P. Garner (Chair of the Committee, Department of Chemistry, CWRU) Prof. Anthony J. Pearson (Department of Chemistry, CWRU) Prof. Fred L. Urbach (Department of Chemistry, CWRU) Dr. Zwong-Wu Guo (Department of Chemistry, CWRU) Dr. Stuart J. Rowan (Department of Macromolecular Science and Engineering, CWRU) Date: 14th January 2005 *We also certify that written approval has been obtained for any propriety material contained therein. To Amma, Naina & all my Teachers Table of Contents List of Tables………………………………………………………………………..……iv List of Figures…………………………………………………………………….…........vi List of Schemes…………………………………………………………………….….….ix List of Equations………………………………………………………...……….……….xi Acknowledgements………………………………………………………….…..……….xii List of Abbreviations……………………………………………………………………xiv Abstract………………………………………………………………………………….xvi CHAPTER I........................................................................................................................ 1 I.1 Structure and Bonding ...........................................................................................
  • United States Patent Office Paiented Sept

    United States Patent Office Paiented Sept

    3,151,173 United States Patent Office Paiented Sept. 29, 1964 i 2 p-toluene sulfonic acid (which is the preferred catalyst 3,151,173 of the present invention). Weaker acids, having first EPOCESS FOR PRGEJCNG SALKY DENE pixa values above 2.5, are less effective. The second class NGREORNENE - Sasks. Tyce, RAS Creek H.Rindred, e., assignor to E. E. of catalysts includes compounds Sugh as boron trifluoride, di Post de NextGE's and Copany, Wisnington, Dei, boron trichloride, aluminum chloride, aluminum bromide, a corporation of Delaware Zinc chloride, titanium tetrachloride, ferric chloride, ferric Na Drawing. Fied Jay 8, 1961, Ser. No. 24,783 bromide, stannic chloride, antimony pentachloride, ni f6 (Cairns. (C. 268-666) obium tetrachloride, tellurium dichloride, bismuth tri chloride, mercuric chioride, and tantulum tetrachloride. This invention relates to a new method for the prepara O The Friedel-Crafts catalysts tend to induce polymeriza tion of Substituted norbornene compounds. More par tion which is evidenced by a darkening of the reaction ticularly this invention relates to a new method of pre mixture. It is preferred to stop the reaction when this paring 5-alkylidene-noirborneine compounds. discoloration occurs. Certain norbornene compounds have been found to The catalyst concentration may range from about be very useful for the preparation of ethylene copolymers. 0.0025 mole to 2.5 mole per mole of the 2-alkylnorborna Jinfortunately, the present methods for the preparation diene compound. The preferred concentration often. f these norbornene compounds, such as 5-methylene ranges from about 0.02 mole to 0.04 mole. However, norbornere, are rather costly and thereby restrict the use When catalysts are used, such as hydrogen chloride, fulness of such compounds in commercial production.
  • High-Level Studies of the Ionic States of Norbornadiene and Quadricyclane

    High-Level Studies of the Ionic States of Norbornadiene and Quadricyclane

    High-level studies of the ionic states of norbornadiene and quadricyclane, including analysis of new experimental photoelectron spectra by configuration interaction and coupled cluster calculations. Michael H. Palmer,1,a Marcello Coreno,2,b Monica de Simone,3,b Cesare Grazioli,3,b R. Alan Aitken,4 Søren Vrønning Hoffmann,5,b Nykola C. Jones5,b and Coralyse Peureux.4 1 School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland, UK 2 ISM-CNR, Istituto di Struttura della Materia, LD2 Unit 34149 Trieste, Italy, 3 IOM-CNR Laboratorio TASC, Trieste, Italy 4 School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, Scotland, UK. 5 ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000, Aarhus C, Denmark a) Email: [email protected]: b) Electronic addresses: [email protected]; [email protected]; [email protected]; [email protected]; [email protected]; [email protected]; [email protected] ABSTRACT Synchrotron-based photoelectron spectra (PES) of norbornadiene (NBD) and quadricyclane (QC) differ significantly from previous studies. The adiabatic ionization energy (AIE1) for 2 NBD, assigned to the B1 state at 8.279 eV, shows a progression of 18 members, with decreasing vibration frequency from 390 to 340 cm-1; our calculated frequency is 381 cm-1. 2 Similarly, the AIE1 for QC at 7.671 eV, assigned to the B2 state, discloses a vibrational progression of 9 or more members, with vibration frequency decreasing from 703 to 660 cm-1; Our calculated vibration frequency is 663 cm-1.
  • Cr(CO)6 System, While for the Mo(CO)6 and W(CO)E

    Cr(CO)6 System, While for the Mo(CO)6 and W(CO)E

    The photochemistry of M(CO)6 and (rj6-pyridine)Cr(CO )3 (M = Cr, Mo, or W) and related systems. This thesis is presented to Dublin City University for the degree, Doctor of Philosophy, by Ciara Breheny BSc Supervisor Dr Conor Long School of Chemical Sciences, Dublin City University 1996 Declaration This thesis has not been submitted as an exercise for a degree at this or at any other university. Except as otherwise stated, this work has been carried out by the author alone. Signed Ciara Breheny. Dedication This thesis is dedicated to my family, Mum, Dad, Conor, and Saibh HI Acknowledgements I would like to say a most sincere thank you to all the following people, Dr Conor Long, for his constant support, help, and advice over the past few years All members past and present of the CLRG, namely Irene, Mick, Maureen, Celia, Mary, Siobhan, and Deirdre Everyone in AG07 who made the past few years enjoyable and unforgettable All members of the chemistry department, especially the technicians, who were always at hand to help when a problem arose (as it invariably did) A word of thanks to my friends outside DCU without whom the past few years would not have been the same, namely, Mane, Ger, Siobhan, Orla, Greg, Ciaran, Shivaun, Ciara, Teresa, Monica, Susan, Bronagh, Anna, Dawn, and Fiona Also a special thanks to Paul for his support over the past year Finally, to my family for their never-ending patience with the seemingly endless student life I have undertaken Without their love and support these past few years would have been a lot more difficult
  • Alkyl and Fluoroalkyl Manganese Pentacarbonyl Complexes As

    Alkyl and Fluoroalkyl Manganese Pentacarbonyl Complexes As

    En vue de l'obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par : Institut National Polytechnique de Toulouse (Toulouse INP) Discipline ou spécialité : Chimie Organométallique et de Coordination Présentée et soutenue par : M. ROBERTO MORALES CERRADA le jeudi 15 novembre 2018 Titre : Complexes de manganèse pentacarbonyle alkyle et fluoroalkyle comme modèles d'espèces dormantes de l'OMRP Ecole doctorale : Sciences de la Matière (SDM) Unité de recherche : Laboratoire de Chimie de Coordination (L.C.C.) Directeur(s) de Thèse : MME FLORENCE GAYET M. BRUNO AMEDURI Rapporteurs : M. GERARD JAOUEN, UNIVERSITE PARIS 6 Mme SOPHIE GUILLAUME, CNRS Membre(s) du jury : M. MATHIAS DESTARAC, UNIVERSITE TOULOUSE 3, Président M. BRUNO AMEDURI, CNRS, Membre M. HENRI CRAMAIL, INP BORDEAUX, Membre Mme FLORENCE GAYET, INP TOULOUSE, Membre A mi abuelo Antonio ‐ i ‐ ‐ ii ‐ Remerciements Ce travail a été réalisé dans deux unités de recherche du CNRS : le laboratoire de Chimie de Coordination (LCC) à Toulouse, au sein de l’équipe LAC2, et l’Institut Charles Gerhardt de Montpellier (ICGM), au sein de l’équipe IAM. Il a été codirigé par Dr. Florence Gayet et Dr. Bruno Améduri. Je tiens tout d’abord à remercier Dr. Azzedine Bousseksou, directeur du LCC, et Dr. Patrick Lacroix‐Desmazes, directeur de l’équipe IAM à l’ICGM, pour avoir accepté de m’accueillir au sein de ses laboratoires. Je remercie tout particulièrement mes directeurs de thèse, Dr. Florence Gayet et Dr. Bruno Améduri, pour m’avoir encadré durant ces trois années de doctorat. Un immense merci à tous les deux pour tous leurs conseils, leur patience et leurs connaissances qui m’ont apporté et qui m’ont permis de mener à bien ce travail.
  • Organometallic and Catalysis

    Organometallic and Catalysis

    ORGANOMETALLIC AND CATALYSIS Dr. Malay Dolai, Assistant Professor, Department of Chemistry, Prabhat Kumar College, Contai, Purba Medinipur-721404, WB, India. 1.Introduction Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and tin, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. In 1827, Zeise's salt is the first platinum- olefin complex: K[PtCl3(C2H4)].H2O, the first invented organometallic compound. Organometallic compounds find wide use in commercial reactions, both as homogeneous catalysis and as stoichiometric reagents For instance, organolithium, organomagnesium, and organoaluminium compounds, examples of which are highly basic and highly reducing, are useful stoichiometrically, but also catalyze many polymerization reactions. Almost all processes involving carbon monoxide rely on catalysts, notable examples being described as carbonylations. The production of acetic acid from methanol and carbon monoxide is catalyzed via metal carbonyl complexes in the Monsanto process and Cativa process. Most synthetic aldehydes are produced via hydroformylation. The bulk of the synthetic alcohols, at least those larger than ethanol, are produced by hydrogenation of hydroformylation- derived aldehydes.
  • Summaries of FY 1997 Research in the Chemical Sciences

    Summaries of FY 1997 Research in the Chemical Sciences

    DOE/NBM-1098 Rev.-1 September 1997 T O EN FE TM N R E A R P G E Y D U • • A N C I I T R E D E M ST A ATES OF Summaries of FY 1997 Research in the Chemical Sciences U.S. Department of Energy Office of Energy Research Division of Chemical Sciences A searchable version of this summary book is available at the following web address: http://websrv.er.doe.gov/asp/search.asp This search tool is also accessible from the Chemical Sciences web page at: http://www.er.doe.gov/production/bes/chm/chmhome.html Available to DOE and DOE contractors from the Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831; prices available from (423) 576-8401 Available to the public from the U.S. Department of Commerce, Technology Administration, National Technical Information Service, Springfield, VA 22161 This document was produced under contract number DE-AC05-76OR00033 between the U.S. Department of Energy and Oak Ridge Associated Universities. ORISE 97-1555 CONTENTS CONTENTS PREFACE ........................................................................ vii Oak Ridge National Laboratory.............................. 42 DIVISION OF CHEMICAL SCIENCES ..................... viii Pacific Northwest National Laboratory .................. 44 PROGRAM DESCRIPTIONS ........................................ ix Heavy Element Chemistry ....................................... 45 LABORATORY ADMINISTRATION ......................... xiii Argonne National Laboratory ................................. 45 Lawrence Berkeley National Laboratory...............
  • Synthesis, Characterization and Metal Carbonyl Complex Formation of Polycyclic Phosphorus Ligands Arthur Cyril Vandenbroucke Jr

    Synthesis, Characterization and Metal Carbonyl Complex Formation of Polycyclic Phosphorus Ligands Arthur Cyril Vandenbroucke Jr

    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1967 Synthesis, characterization and metal carbonyl complex formation of polycyclic phosphorus ligands Arthur Cyril Vandenbroucke Jr. Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Vandenbroucke, Arthur Cyril Jr., "Synthesis, characterization and metal carbonyl complex formation of polycyclic phosphorus ligands " (1967). Retrospective Theses and Dissertations. 3219. https://lib.dr.iastate.edu/rtd/3219 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]. This dissertation has been microfihned exactly as received 68-5990 VANDENBROUCKE, Jr., Arthur Cyril, 1941- SYNTHESIS, CHARACTERIZATION AND METAL CARBONYL COMPLEX FORMATION OF POLYCYCLIC PHOSPHORUS LIGANDS. Iowa State University, Ph.D,, 1967 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan . .SYNTHESISJ CHARACTERIZATION AND METAL CARBONYL COMPLEX FORMATION OF POLYCYCLIC PHOSPHORUS LIGANDS by Arthur Cyril Vandenbroucke, Jr. A -Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Inorganic Chemistry • Approved: Signature was redacted for privacy. argë of Major Work Signature was redacted for privacy. Head of Major DepartmentDepart Signature was redacted for privacy. Iowa State University •Of Science and Technology Ames J Iowa 1967 il TABLE OF CONTENTS Pagé I. INTRODUCTION 1 II. A STUDY OF THE SYNTHESIS OF 1-PHOSPHAADAMANTANE 2 A.
  • United States Patent Office Patented Apr

    United States Patent Office Patented Apr

    3,381,023 United States Patent Office Patented Apr. 30, 1968 1. 2 Furthermore, the isolation procedures for separating the 3,381,023 resulting compounds are simplified by the process of this PREPARATION OF AROMATIC GROUP VI-B METAL TRICARBONYS invention, as a minimum of unreacted starting materials Mark Crosby Whiting, Oxford, England, assignor to and side products are present in the final composition. In Ethyl Corporation, New York, N.Y., a corpora addition, Superior yields are obtained. For example, tion of Virginia O-cresyl methylether chromium tricarbonyl was prepared No Drawing. Filed Mar. 10, 1958, Ser. No. 720,083 in 99 percent yield by the process of this invention. Yields 31 Claims. (Ci. 260-429) of this order of magnitude have not heretofore been pos sible. This invention relates to a process for the preparation The temperatures employed in the process of this inven of organometallic compounds and more particularly the O tion may vary over a wide range. In general, tempera preparation of aromatic Group VI-B transition metal tures of from about 100° C. to 300° C. are employed. carbonyl compounds. However, a preferred range of temperature is from Recently a method for the preparation of aromatic 150 C. to 225 C. as the reaction in this temperature chromium tricarbonyl compounds has been proposed, 5 range leads to a high yield of products with a minimum which method comprises the equilibration, in an aromatic of undesirable side reactions. Solvent of a di-aromatic chromium compound with chro The aromatic compound which is a reactant in the mium hexacarbonyl and which employs a reaction time process of this invention can be selected from a wide of 12 hours under pressure at temperature in excess of range of aromatic organic compounds including mono 200 C.
  • Metal Carbonyls

    Metal Carbonyls

    MODULE 1: METAL CARBONYLS Key words: Carbon monoxide; transition metal complexes; ligand substitution reactions; mononuclear carbonyls; dinuclear carbonyls; polynuclear carbonyls; catalytic activity; Monsanto process; Collman’s reagent; effective atomic number; 18-electron rule V. D. Bhatt / Selected topics in coordination chemistry / 2 MODULE 1: METAL CARBONYLS LECTURE #1 1. INTRODUCTION: Justus von Liebig attempted initial experiments on reaction of carbon monoxide with metals in 1834. However, it was demonstrated later that the compound he claimed to be potassium carbonyl was not a metal carbonyl at all. After the synthesis of [PtCl2(CO)2] and [PtCl2(CO)]2 reported by Schutzenberger (1868) followed by [Ni(CO)4] reported by Mond et al (1890), Hieber prepared numerous compounds containing metal and carbon monoxide. Compounds having at least one bond between carbon and metal are known as organometallic compounds. Metal carbonyls are the transition metal complexes of carbon monoxide containing metal-carbon bond. Lone pair of electrons are available on both carbon and oxygen atoms of carbon monoxide ligand. However, as the carbon atoms donate electrons to the metal, these complexes are named as carbonyls. A variety of such complexes such as mono nuclear, poly nuclear, homoleptic and mixed ligand are known. These compounds are widely studied due to industrial importance, catalytic properties and structural interest. V. D. Bhatt / Selected topics in coordination chemistry / 3 Carbon monoxide is one of the most important π- acceptor ligand. Because of its π- acidity, carbon monoxide can stabilize zero formal oxidation state of metals in carbonyl complexes. 2. SYNTHESIS OF METAL CARBONYLS Following are some of the general methods of preparation of metal carbonyls.
  • The Photochemistry of Some Substituted 2-Cyclohexenones and the Excited States Involved

    The Photochemistry of Some Substituted 2-Cyclohexenones and the Excited States Involved

    PHOTOCHEMISTRY OF SUBSTITUTi':D 2... CYCLOHE:XE;NONES THE PHOTOCHEMISTRY OF S0~1E SUBSTITUTED 2~CYCLOHEXENONES AND THE EXCITED STATES INVOLVED By FLOlTI FP~ERICK SNYDER, B.Sce .A Thesis Submitted to the Faculty of Graduate Studies in Partial Fulfilment of the Requirements for the Degree Master of Science McMaster University October 1969 To MOM and DAD on Your 25th Anniversary MASTER OF SCIENCE (1969) McMASTER UNIVERSITY (Ghemi stry) Hamilton, Ontario. TITLE: The Photochemistry of some Substituted 2-Cyclohexenones and the Excited States Involved AUTHOR: Floyd Frederick Snyder, B.Sc. '(University of Alberta) SUPERVISOR: Dr. J. J. McCullough NUMBER OF PAGES: viii, 87 SCOPE AND CONTENTS: The photoadditions of 3~phenyl-2-cyclohexenone to bicyclo [2.2.1] ­ hepta-2,5-diene, bicyclo [2.2.1] hept-2mene and cyclopentene have been studied. In all cases £.!1! fused cyclobutane products were obtained. Quenching and sensitization experiments indicated a singlet excited state to be active in photocycloaddition. Phosphorescence and fluorescence emission were observed from 3-phenyl-2-cyclohexenoneo Energy transfer to the lo~.rest triplet of 3-phenyl-2-cyclohexenone was evident from the quenching of Michler's ketone phosphorescence. Two norbornene dimers were detected in the photolysis of 3-phenyl-2-cyclo­ hexenone and norbornene giving evidence for a higher triplet excited state of the enone. The photoaddition of 3-methyl-2-cyclohexenone to cyclopentene l.ras studied for comparison and both .£!..! and !.r..!.U! fused adducts l-Tere obtained. In photolyses with bicyclo [2e2el] hepta-2,5­ diene or cyclopentene, 2-phenyl... 2-cyclohexenone lvas unreactive. iii ACKNOWLEDGEMENTS It is a pleasure to express my gratitude to Dr.
  • Specialty Silicones Norbornadiene Technical Data

    Specialty Silicones Norbornadiene Technical Data

    SiVance® Specialty Silicones Norbornadiene Technical Data Description Typical Properties SiVance Norbornadiene Product Code 3000064155 (bicyclo[2.2.1]hepta-2,5- diene) is an unsaturated, CAS Number 121-46-0 bicyclic hydrocarbon. Molecular Weight (g/mol) 92.14 Recommended Use Specific Gravity, at 25°C 0.91 Norbornadiene is used in the synthesis of complex Boiling Point 89°C polycyclic hydrocarbons. Flash Point, TCC -21°C This hydrocarbon is the most stable diolefin derived from the norbornane and norbornene. Purity 99.5% Norbornadiene is primarily of interest as a ligand Appearance Clear Faint Yellow Liquid in homogeneous catalysis, but it has been heavily studied due to its high reactivity and distinctive Values shown are not intended for specification preparation structural property of being a diene that cannot isomerize. Handling and Storage Precautions If stored for longer than one year, the material should be reevaluated prior to use. Store the container in a cool, dry area. Keep the container tightly closed when not in use. Additional safety, environmental and regulatory issues are addressed in the Safety Data Sheet. Please contact your SiVance Representative for additional information. PLEASE NOTE: As each customer’s use of our product may be different, information we provide, including without limitation, recommendations, test results, samples, care/labeling/processing instructions or marketing advice, is provided in good faith but without warranty and without accepting any responsibility/liability. Each customer must test and be responsible for its own specific use, further processing, labeling, marketing, etc. All sales are exclusively subject to our standard terms of sale posted at www.milliken.com/terms (all additional/different terms are rejected) unless explicitly agreed otherwise in a signed writing.