CHEM 426/626 Reactive Intermediates

Total Page：16

File Type：pdf, Size：1020Kb

CHEM 426/626 Reactive Intermediates According to Concordia’s Centre for Teaching and Learning Services: F un C ommunity I nteresting L esson plan R ules A xpectations S yllabus S upport T est (pre-) S mile Typical class grade distribution in the past Grades Winter 03 (26-6/20) Mark range UG Grad 0-49 F F 7 6 50 - 52 D- F 6 53 - 56 D F 5 4 4 57 - 59 D+ F 4 60 - 62 C- F 3 2 22 2 63 - 66 C C 2 11 1 1 67 - 69 C+ C 1 0 0 70 - 72 B- B- 0 A+ A A- B+ B B- C+ C C- D+ D D- F 73 - 76 B B 77 - 79 B+ B+ 80 - 85 A- A- 86 - 92 A A 1 grad regular great 1 grad 93 - 100 A+ A+ 3 undergrads practice presentation 1 undergrad and reading Who needs to know about reactive intermediates? 1. The chemist 2. The biochemist Singlet O2 Feat Nitric Oxide Battles Tuberculosis Simple, nonchiral molecule resolves racemates Experimental drugs release NO, which kills with surprising selectivity dormant as well as active tuberculosis cells Maureen Rouhi Sophie L. Rovner J. Am. Chem. Soc. 2004, 126, 10498. The paper Science 2008, 322, 1392. Release of the highly "reveals truly remarkable effects" of experimental reactive NO is "akin to a bomb blast that kills the parameters on the stereoselectivity, comments bacteria from within," says Clifton E. Barry III of Miguel A. Garcia-Garibay, a chemistry professor at the National Institute of Allergy & Infectious the University of California, Los Angeles. Diseases, in Bethesda, Md. C&E News December 1, 2008 C&E News August 23, 2004 2. The biochemist continued Pseudomonas putida P450 (P450cam) P450 from the soil bacterium P. putida is best characterized. The bacterium degrades camphor O P450cam O - + to obtain a carbon source for energy. First step: 2e , O2, 2H OH Something odd here?! Mechanism of alkane hydroxylation substrate-bound form Sono et al., Chem. Rev. 2850, 96 (1996) Nobel prizes The ultimate prize for recognizing what is “important”. 1967 (Manfred Eigen), Ronald Norrish, George Porter for their studies of extremely fast chemical reactions, effected by disturbing the equlibrium by means of very short pulses of energy (flash photolysis) 1971 Gerhard Herzberg for his contributions to the knowledge of electronic structure and geometry of molecules, particularly free radicals http://nobelprize.org/chemistry/laureates/ Nobel prizes 1994 George Olah for his contribution to carbocation chemistry 1999 Ahmed Zewail for his studies of the transition states of chemicalical reactionsreactions using femtosecond spectroscopy http://nobelprize.org/chemistry/laureates/ Reactive Intermediates CHEM 426/626 Some introduction Science has always strived to see smaller and smaller things and faster and faster events. Bengt Nordén, Presentation Speech, The Nobel Prize in Chemistry 1999 (Zewail) • Which reactive intermediates do you know? mechanisms! • How are they formed? breaking bonds • Here we are (mostly) interested in carbon species. carbon valencies • Which common molecules could be considered reactive intermediates?.

Copy Link

Recommended publications

The Beckman Center for the History of Chemistry
THE BECKMAN CENTER FOR THE HISTORY OF CHEMISTRY GERHARD HERZBERG Transcript of an Interview Conducted by M. Christine King at The National Research Council of Canada on 5 May 1986 This interview has been designated as Free Access. One may view, quote from, cite, or reproduce the oral history with the permission of CHF. Please note: Users citing this interview for purposes of publication are obliged under the terms of the Chemical Heritage Foundation Oral History Program to credit CHF using the format below: Gerhard Herzberg, interview by M. Christine King at The National Research Council of Canada, Ottawa, Canada, 5 May 1986 (Philadelphia: Chemical Heritage Foundation, Oral History Transcript # 0023). Chemical Heritage Foundation Oral History Program 315 Chestnut Street Philadelphia, Pennsylvania 19106 The Chemical Heritage Foundation (CHF) serves the community of the chemical and molecular sciences, and the wider public, by treasuring the past, educating the present, and inspiring the future. CHF maintains a world-class collection of materials that document the history and heritage of the chemical and molecular sciences, technologies, and industries; encourages research in CHF collections; and carries out a program of outreach and interpretation in order to advance an understanding of the role of the chemical and molecular sciences, technologies, and industries in shaping society. GERHARD HERZBERG 1904 Born in Hamburg, Germany on 25 December Education 1928 Dr. Ing., Darmstadt Technische Universität Professional Experience 1928-1929 Post-doctoral
[Show full text]
New 78 Covers
NATIONAL ACADEMY OF SCIENCES ROBERT SANDERSON MULLIKEN 1896–1986 A Biographical Memoir by R. STEPHEN BERRY Biographical Memoirs, VOLUME 78 PUBLISHED 2000 BY THE NATIONAL ACADEMY PRESS WASHINGTON, D.C. Photo credit: Photo by Harris & Ewing, Washington, D.C. ROBERT SANDERSON MULLIKEN June 7, 1896-October 31, 1986 BY R. STEPHEN BERRY OBERT S. MULLIKEN WAS a quiet, soft-spoken man, yet so R single-minded and determined in his devotion to under- standing molecules that he came to be called “Mr. Molecule.” If any single person’s ideas and teachings dominated the development of our understanding of molecular structure and spectra, it surely was Robert Mulliken. From the begin- ning of his career as an independent scientist in the mid- 1920s until he published his last scientific papers in the early 1980s, he guided an entire field through his penetrat- ing solutions of outstanding puzzles, his identification (or discovery) and analysis of the new major problems ripe for study, and his creation of a school—the Laboratory of Molecular Structure and Spectroscopy or LMSS at the University of Chicago, during its existence the most impor- tant center in the world for the study of molecules. Robert’s background led him naturally into academic sci- ence. He was born in Newburyport, Massachusetts, in a house built by his great-grandfather in about 1798. His father, Samuel Parsons Mulliken, was a professor of chemistry at MIT, which made him a daily commuter between Newburyport and Boston. Samuel Mulliken and his child- hood friend and later MIT colleague Arthur A. Noyes were 3 4 BIOGRAPHICAL MEMOIRS strong influences stirring Robert’s interests in science.
[Show full text]
Henry Taube Papers SC0731SC0731
http://oac.cdlib.org/findaid/ark:/13030/kt329035mg No online items Guide to the Henry Taube Papers SC0731SC0731 Stanford University Archives staff Department of Special Collections and University Archives October 2010 Green Library 557 Escondido Mall Stanford 94305-6064 [email protected] URL: http://library.stanford.edu/spc Note This encoded finding aid is compliant with Stanford EAD Best Practice Guidelines, Version 1.0. Guide to the Henry Taube Papers SC073117755 1 SC0731SC0731 Language of Material: English Contributing Institution: Department of Special Collections and University Archives Title: Henry Taube papers Creator: Taube, Henry Identifier/Call Number: SC0731 Identifier/Call Number: 17755 Physical Description: 65.25 Linear Feet(56 boxes) Date (inclusive): 1941-2003 Abstract: Collection pertains to his teaching and research, primarily while at Stanford University, and includes grant files, articles and papers, reprints, class files, correspondence, travel records, and biographical materials. Information about Access This collection is open for research; materials must be requested at least 48 hours in advance of intended use. Ownership & Copyright All requests to reproduce, publish, quote from, or otherwise use collection materials must be submitted in writing to the Head of Special Collections and University Archives, Stanford University Libraries, Stanford, California 94304-6064. Consent is given on behalf of Special Collections as the owner of the physical items and is not intended to include or imply permission from the copyright owner. Such permission must be obtained from the copyright owner, heir(s) or assigns. See: http://library.stanford.edu/depts/spc/pubserv/permissions.html. Restrictions also apply to digital representations of the original materials.
[Show full text]
George Porter
G EORGE P O R T E R Flash photolysis and some of its applications Nobel Lecture, December 11, 1967 One of the principal activities of man as scientist and technologist has been the extension of the very limited senses with which he is endowed so as to enable him to observe phenomena with dimensions very different from those he can normally experience. In the realm of the very small, microscopes and micro- balances have permitted him to observe things which have smaller extension or mass than he can see or feel. In the dimension of time, without the aid of special techniques, he is limited in his perception to times between about one twentieth of a second ( the response time of the eye) and about 2·10 9 seconds (his lifetime). Y et most of the fundamental processes and events, particularly those in the molecular world which we call chemistry, occur in milliseconds or less and it is therefore natural that the chemist should seek methods for the study of events in microtime. My own work on "the study of extremely fast chemical reactions effected by disturbing the equilibrium by means of very short pulses of energy" was begun in Cambridge twenty years ago. In 1947 I attended a discussion of the Faraday Society on "The Labile Molecule". Although this meeting was en- tirely concerned with studies of short lived chemical substances, the four hundred pages of printed discussion contain little or no indication of the im- pending change in experimental approach which was to result from the intro- .
[Show full text]
Robert Mulliken
NATIONAL ACADEMY OF SCIENCES ROBERT SANDERSON MULLIKEN 1896–1986 A Biographical Memoir by R. STEPHEN BERRY Biographical Memoirs, VOLUME 78 PUBLISHED 2000 BY THE NATIONAL ACADEMY PRESS WASHINGTON, D.C. Photo credit: Photo by Harris & Ewing, Washington, D.C. ROBERT SANDERSON MULLIKEN June 7, 1896-October 31, 1986 BY R. STEPHEN BERRY OBERT S. MULLIKEN WAS a quiet, soft-spoken man, yet so R single-minded and determined in his devotion to under- standing molecules that he came to be called “Mr. Molecule.” If any single person’s ideas and teachings dominated the development of our understanding of molecular structure and spectra, it surely was Robert Mulliken. From the begin- ning of his career as an independent scientist in the mid- 1920s until he published his last scientific papers in the early 1980s, he guided an entire field through his penetrat- ing solutions of outstanding puzzles, his identification (or discovery) and analysis of the new major problems ripe for study, and his creation of a school—the Laboratory of Molecular Structure and Spectroscopy or LMSS at the University of Chicago, during its existence the most impor- tant center in the world for the study of molecules. Robert’s background led him naturally into academic sci- ence. He was born in Newburyport, Massachusetts, in a house built by his great-grandfather in about 1798. His father, Samuel Parsons Mulliken, was a professor of chemistry at MIT, which made him a daily commuter between Newburyport and Boston. Samuel Mulliken and his child- hood friend and later MIT colleague Arthur A. Noyes were 3 4 BIOGRAPHICAL MEMOIRS strong influences stirring Robert’s interests in science.
[Show full text]
Manfred Eigen: the Realization of His Vision of Biophysical Chemistry
CORE Metadata, citation and similar papers at core.ac.uk Provided by OIST Institutional Repository Manfred Eigen: the realization of his vision of Biophysical Chemistry Author Herbert Jackle, Carmen Rotte, Peter Gruss journal or European Biophysics Journal publication title volume 47 number 4 page range 319-323 year 2017-12-11 Publisher Springer International Publishing Rights (C) 2017 The Author(s). Author's flag publisher URL http://id.nii.ac.jp/1394/00000696/ doi: info:doi/10.1007/s00249-017-1266-y Creative Commons Attribution 4.0 International (http://creativecommons.org/licenses/by/4.0/) European Biophysics Journal (2018) 47:319–323 https://doi.org/10.1007/s00249-017-1266-y REVIEW Manfred Eigen: the realization of his vision of Biophysical Chemistry Herbert Jäckle1 · Carmen Rotte1 · Peter Gruss1,2 Received: 27 August 2017 / Accepted: 11 November 2017 / Published online: 11 December 2017 © The Author(s) 2017. This article is an open access publication Abstract Manfred Eigen turned 90 on May 9th, 2017. He celebrated with a small group of colleagues and friends on behalf of the many inspired by him over his lifetime—whether scientists, artists, or philosophers. A small group of friends, because many—who by their breakthroughs have changed the face of science in diferent research areas—have already died. But it was a special day, devoted to the many genius facets of Manfred Eigen’s oeuvre, and a day to highlight the way in which he continues to exude a great, vital and unbroken passion for science as well as an insatiable curiosity beyond his own scientifc interests.
[Show full text]
Henry Taube by J
Chemical Education Today Nobel Centennial Essays A Century of Chemical Dynamics Traced through the Nobel Prizes W 1983: Henry Taube by J. Van Houten Nobel Prize in Chemistry 1983 Photo by Rudy Baum Henry Taube (1915– ) for his work on the mechanisms of electron transfer Henry Taube, shown on reactions, especially in metal complexes the cover of C&E News. This is the eighth in a series of essays (1) written in com- Reprinted with permis- memoration of the centennial of the Nobel Prize, examin- sion from Chemical & ing the history of chemical dynamics in the 20th century.W Engineering News, May 21, 1984. © As his Nobel citation (2) states, Henry Taube studied elec- Copyright 1984 Ameri- tron transfer reactions of transition metal complexes. The can Chemical Society. Nobel Prize to Taube came exactly seventy years after it was awarded to Alfred Werner (3) for developing the structural chemistry of inorganic transition metal complexes. During the entire 20th century, Taube and Werner are the only in- to Werner’s. His early mechanistic studies relied heavily on organic transition metal chemists to win a Nobel Prize.1 In isotope tracer techniques developed by George de Hevesy, the fact, many of the complexes that Taube studied were first 1943 Nobel Laureate (1d). The second of the 100 references prepared or characterized by Werner. in Taube’s Nobel lecture (6) is to a 1920 paper where de Taube’s citation (2) concludes with the statement: “There Hevesy used naturally occurring lead isotopes to follow the is no doubt that Henry Taube is one of the most creative exchange reaction between Pb2+ and Pb4+ (7).
[Show full text]
Walter Elsasser in Mind
NATIONAL ACADEMY OF SCIENCES W A L T E R M . E LSASSER 1904—1991 A Biographical Memoir by H A R R Y RU BIN Any opinions expressed in this memoir are those of the author(s) and do not necessarily reflect the views of the National Academy of Sciences. Biographical Memoir COPYRIGHT 1995 NATIONAL ACADEMIES PRESS WASHINGTON D.C. WALTER M. ELSASSER March 20, 1904–October 14, 1991 BY HARRY RUBIN ALTER ELSASSER WAS TRAINED as a theoretical physicist Wand made several important contributions to funda- mental problems of atomic physics, including interpreta- tion of the experiments on electron scattering by Davisson and Germer as an effect of de Broglie’s electron waves and recognition of the shell structure of atomic nuclei. Circum- stances later turned his interests to geophysics, where he had important insights about the radiative transfer of heat in the atmosphere and fathered the generally accepted dy- namo theory of the earth’s magnetism. He devoted a major part of the last fifty years of his life to developing a theory of organisms, concentrating on the basic features that dis- tinguish between living and inanimate matter, and he pro- duced four books on the subject. While his contribution to biology was not widely acknowledged, he felt it would even- tually be seen as his major scientific achievement. BACKGROUND AND YOUTH Walter was born in Mannheim, Germany, the older of two children of Maurice and Johanna Elsasser. His sister, Maria, was three years younger than him. His grandparents were prosperous Jewish merchants, but his father was a law- 103 104 BIOGRAPHICAL MEMOIRS yer who was caught up in the great wave of assimilation and both parents became nonpracticing Protestants.
[Show full text]
Gerhard Herzberg
The Nobel Prize in Chemistry 1971 Gerhard Herzberg Gerhard Herzberg Born: 25 December 1904, Hamburg, Germany Died: 3 March 1999, Ottawa, Canada Affiliation at the time of the award: National Research Council of Canada, Ottawa, Canada Prize motivation: "for his contributions to the knowledge of electronic structure and geometry of molecules, particularly free radicals" Field: Physical chemistry, molecular structures Information taken from The Official Website of the Nobel Prize nobelprize.org “…series of bands with complicated fine structure in the red and photographic infrared… This spectrum was analysed as that of an asymmetric top…” (1) Geometrical structure of CH2 in the three lowest states (1) Spectra and quotes from the Nobel Lecture by G. Herzberg The Nobel Prize in Physics 1918 Max Planck Max Karl Ernst Ludwig Planck Born: 23 April 1858, Kiel, Schleswig (now Germany) Died: 4 October 1947, Goettingen, West Germany Affiliation at the time of the award: Berlin University,Berlin, Germany Prize motivation: "in recognition of the services he rendered to the advancement of Physics by his discovery of energy quanta" Field: Quantum mechanics Max Planck received his Nobel Prize one year later, in 1919. Information taken from The Official Website of the Nobel Prize nobelprize.org The Nobel Prize in Physics 1922 Niels Bohr Niels Henrik David Bohr Born: 7 October 1885, Copenhagen, Denmark Died: 18 November 1962, Copenhagen, Denmark Affiliation at the time of the award: Copenhagen University, Copenhagen, Denmark Prize motivation: "for his services
[Show full text]
Report for the Academic Year 1999
l'gEgasag^a3;•*a^oggMaBgaBK>ry^vg^.g^._--r^J3^JBgig^^gqt«a»J^:^^^^^ Institute /or ADVANCED STUDY REPORT FOR THE ACADEMIC YEAR 1998-99 PRINCETON • NEW JERSEY HISTORICAL STUDIES^SOCIAl SC^JCE LIBRARY INSTITUTE FOR ADVANCED STUDY PRINCETON, NEW JERSEY 08540 Institute /or ADVANCED STUDY REPORT FOR THE ACADEMIC YEAR 1 998 - 99 OLDEN LANE PRINCETON • NEW JERSEY • 08540-0631 609-734-8000 609-924-8399 (Fax) http://www.ias.edu Extract from the letter addressed by the Institute's Founders, Louis Bamberger and Mrs. FeUx Fuld, to the Board of Trustees, dated June 4, 1930. Newark, New Jersey. It is fundamental m our purpose, and our express desire, that in the appointments to the staff and faculty, as well as in the admission of workers and students, no account shall be taken, directly or indirectly, of race, religion, or sex. We feel strongly that the spirit characteristic of America at its noblest, above all the pursuit of higher learning, cannot admit of any conditions as to personnel other than those designed to promote the objects for which this institution is established, and particularly with no regard whatever to accidents of race, creed, or sex. ni' TABLE OF CONTENTS 4 • BACKGROUND AND PURPOSE 7 • FOUNDERS, TRUSTEES AND OFFICERS OF THE BOARD AND OF THE CORPORATION 10 • ADMINISTRATION 12 • PRESENT AND PAST DIRECTORS AND FACULTY 15 REPORT OF THE CHAIRMAN 18 • REPORT OF THE DIRECTOR 22 • OFFICE OF THE DIRECTOR - RECORD OF EVENTS 27 ACKNOWLEDGMENTS 41 • REPORT OF THE SCHOOL OF HISTORICAL STUDIES FACULTY ACADEMIC ACTIVITIES MEMBERS, VISITORS,
[Show full text]
Nobel Laureates Meet International Top Talents
Nobel Laureates Meet International Top Talents Evaluation Report of the Interdisciplinary Lindau Meeting of Nobel Laureates 2005 Council for the Lindau Nobel Laureate Meetings Foundation Lindau Nobelprizewinners Meetings at Lake Constance Nobel Laureates Meet International Top Talents Evaluation Report of the Interdisciplinary Lindau Meeting of Nobel Laureates 2005 Council for the Lindau Nobel Laureate Meetings Foundation Lindau Nobelprizewinners Meetings at Lake Constance I M PR I N T Published by: Council for the Lindau Nobel Laureate Meetings, Ludwigstr. 68, 88131 Lindau, Germany Foundation Lindau Nobelprizewinners Meetings at Lake Constance, Mainau Castle, 78465 Insel Mainau, Germany Idea and Realisation: Thomas Ellerbeck, Member of the Council for the Lindau Nobel Laureate Meetings and of the Board of Foundation Lindau Nobelprizewinners Meetings at Lake Constance, Alter Weg 100, 32760 Detmold, Germany Science&Media, Büro für Wissenschafts- und Technikkommunikation, Betastr. 9a, 85774 Unterföhring, Germany Texts: Professor Dr. Jürgen Uhlenbusch and Dr. Ulrich Stoll Layout and Production: Vasco Kintzel, Loitersdorf 20a, 85617 Assling, Germany Photos: Peter Badge/typos I, Wrangelstr. 8, 10997 Berlin, Germany Printed by: Druckerei Hermann Brägger, Bankgasse 8, 9001 St. Gallen, Switzerland 2 The Interdisciplinary Lindau Meeting of Nobel Laureates 2005 marked a decisive step for the annual Lindau Meeting in becoming a unique and signiﬁcant international forum for excellence, fostering the vision of its Spiritus Rector, Count Lennart Bernadotte. It brought together, in the heart of Europe, the world’s current and prospective scientiﬁc leaders, the minds that shape the future drive for innovation. As a distinct learning experience, the Meeting stimulated personal dialogue on new discoveries, new methodologies and new issues, as well as on cutting-edge research matters.
[Show full text]
MANFRED EIGEN of the Reaction
M ANFRED E I G E N Immeasurably fast reactions* Nobel Lecture, December 11, 1967 1. "Prejudice and Pride" "The rate of true neutralization reactions has proved to be immeasurably fast". I found this quotation in Eucken’s Lehrbuch der Chemischen Physik I while I was preparing for my doctor’s examination. Although as a student of Eucken, this book was for me the "bible of physical chemistry", I was then at the age when one accepts practically nothing unquestioned, and so I started to reflect on just how fast an "immeasurably fast" reaction might be. Clearly, the two reagents - the H+ and OH- ions in the case of neutrali- zation - must come together before they can combine to form the reaction product: the H 2O molecule. The maximum rate will be determined by the frequency of such encounters or collisions, and this in turn will depend only on the diffusion rate and the mean separation of the reaction partners. This problem had already been analysed by Langevin 2, von Smoluchowski 3, Ein- stein 4, Onsager 5, and Debye 6, all of whom had derived expressions for the frequency of ionic collisions. It was fortunate that I was unable at that time to find in Göttingen Debye’s paper in which this problem is solved in general form, for this meant that I had to sit down and derive again for myself the expression for the rate constant of diffusion-controlled reactions. The result was a theory which also applies to the mechanism of reactions in which not every encounter is successful.
[Show full text]