DOCSLIB.ORG

CHEM 494 Lecture 6

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
CHEM 494 Lecture 6 CHEM 494 University of Illinois Special Topics in Chemistry at Chicago UIC CHEM 494 - Lecture 6 Prof. Duncan Wardrop October 15, 2012 Midterm “Papers” • Factors that Control Hydrocarbon Acidity • Factors that Control Hydrocarbon Conformation • Platonic Hydrocarbons (Cubane and Beyond) • Hydrocarbon Chemistry of Gasoline • Hydrocarbon Chemistry of Anesthesia • Chemistry of the Perfect Pasta Sauce University of Slide CHEM 494, Spring 2010 2 Illinois at Chicago UIC Lecture 6: October 15 CHEM 494 University of Illinois Special Topics in Chemistry at Chicago UIC Nucleophilic Substitution at Saturated Carbon Chapter 19 Structure of Carbocations • carbocations are high energy intermediates; hard, but not impossible to isolate 2pZ • carbon is sp2-hybridized with a single, H unoccupied 2pZ orbital; 6 valence electrons H3C C • planar structure : three bonds to carbon are H at 120º angles from each other and 90º to empty p-orbital; VSEPR • nucleophiles add to either lobe of the empty carbocations can be stabilized by inductive effects and hyperconjugation p-orbital; since it is !at, there is no preference to which side nucleophile adds University of Slide CHEM 494, Spring 2010 4 Illinois at Chicago UIC Lecture 6: October 15 Stability of Carbocations 1. Inductive Effects electron withdrawal or electron donation that is transmitted through σ- bonds; polarization of σ-bonds • electron donation through 1º cation σ-bonds toward δ+ carbocation delocalizes δ+ H charge (spreads out) • C-C σ-bonds are more H3C C polarizable, therefore δ+ donate more electron H density through σ-bonds • more C-C σ-bonds = more stable carbocation University of Slide CHEM 494, Spring 2010 5 Illinois at Chicago UIC Lecture 6: October 15 Stability of Carbocations 1. Inductive Effects Since C-C σ-bonds are more polarizable than C-H bonds, the additional of more alkyl groups leads to stabilization of the cation 2º cation 3º cation δ+ δ+ δ+ CH3 H C C δ+ CH3 3 H3C C H δ+ CH3 δ+ University of Slide CHEM 494, Spring 2010 6 Illinois at Chicago UIC Lecture 6: October 15 Stability of Carbocations 2. Hyperconjugation stabilizing interaction that results from the interaction of the electrons in a σ-bond (C–H or C–C bond ) with an adjacent empty (or partially #lled) orbital. Leads to the formation of an extended molecular orbital that increases the stability of the system filled σ orbital • stabilization results from σ-donation to empty p orbital of planar carbocation empty • electron donation through σ-bonds H p orbital toward carbocation delocalizes charge H (spreads out) C C H H • methyl cations cannot be stabilized by hyperconjugation since σ-bonds are H perpendicular to the empty p orbital 1º cation University of Slide CHEM 494, Spring 2010 7 Illinois at Chicago UIC Lecture 6: October 15 Stability of Carbocations 2. Hyperconjugation filled empty σ orbital 2pZ orbital empty C-H 2pZ H p orbital bonding y (filled) g H r e C C n E H H Stabilization resulting from H σ hyperconjugation University of Slide CHEM 494, Spring 2010 8 Illinois at Chicago UIC Lecture 6: October 15 Stability of Carbocations H H CH3 H H H3C CH2 CH2 CH2 C C C C C C H H H CH2 H CH2 H H H H CH3 H 2º carbocation 3º carbocation 3º carbocation 2 C-H bond 3 C-H bond 3 C-C or C-H bond hyperconjugative hyperconjugative hyperconjugative donors donors donors University of Slide CHEM 494, Spring 2010 9 Illinois at Chicago UIC Lecture 6: October 15 i>Clicker Question Rank the following carbocations in order of increasing stability? A. a,b,c,d a. b. c. d. CH3 H B. c,d,b,a H H C. d,c,a,b H3C C H H H D. b,c,a,d 2º 3º 1º methyl E. d,a,c,b University of Slide CHEM 494, Spring 2010 10 Illinois at Chicago UIC Lecture 6: October 15 Stabilizing Effects on Carbocations • smallest inductive effect • largest inductive effect • no hyperconjugation • most hyperconjugation University of Slide CHEM 494, Spring 2010 11 Illinois at Chicago UIC Lecture 6: October 15 How Carbocation Stability Effects Rate of Reaction • more stable (lower energy) carbocation = • more stable (lower energy) transition state (Hammond Post.) = • lower activation energy (Ea) = • faster reaction University of Slide CHEM 494, Spring 2010 12 Illinois at Chicago UIC Lecture 6: October 15 Why are 1° & 2° Alcohols Less Reactive? H-X EA too high H H O OH H H simple 1° and 2° alcohols do not Ea undergo substitution by the SN1 OH + HCl Ea mechanism since methyl and OH primary carbocations are too high in energy to be intermediates in nucleophilic substitution reactions = transition state RCl + H2O an alternative mechanism is required....... University of Slide CHEM 494, Spring 2010 13 Illinois at Chicago UIC Lecture 6: October 15 Bimolecular Substitution - SN2 Mechanism H fast H H3C O H H3C O Br H3C H H H Br slow (rate-determining) Step 1 ‡ Protonation CH3 δ- H H3C Br + Step 2 Br C O δ+ H H H Nucleophilic Attack H H O • C-O bond breaks at the same time the nucleophile (Br) forms the C-X bond • RDS is nucleophilic attack; bimolecular, therefore Ingold notation = SN2 • fewer steps does not mean faster reaction University of Slide CHEM 494, Spring 2010 14 Illinois at Chicago UIC Lecture 6: October 15 Self Test Question Which rate equation below best describes the rate determining step (RDS) in an SN2 mechanism? H H3C O Br H A. rate = k[oxonium ion] B. rate = k[carbocation] ‡ CH3 δ- H Br C O δ+ C. rate = k[oxonium ion][halide] H H H D. rate = k[carbocation][halide] E. rate = k[alcohol][HX] H3C Br University of Slide CHEM 494, Spring 2010 15 Illinois at Chicago UIC Lecture 6: October 15 CHEM 494 University of Illinois Special Topics in Chemistry at Chicago UIC Halogenation of Alkanes Methods and Mechanism Chapter 39 Halogenation of Alkanes Fluorination (F2): Highly Exothermic (Explosive !) Chlorination (Cl2): Exothermic Bromination (Br2): Slightly Exothermic Reactivity Increasing Increasing Iodination (I2): Endothermic University of Slide CHEM 494, Spring 2010 17 Illinois at Chicago UIC Lecture 6: October 15 Radical Chain Mechanism Step One Initiation via Homolysis homolysis Cl Cl Cl + Cl light (hν) free radical half-headed arrow homolysis heterolysis “"shhook” (homolytic cleavage) (heterolytic cleavage) unpaired electron; stabilized by same movement of a single cleavage of a covalent cleavage of a covalent factors that stabilized electron, not a pair bond so that each atom bond so that one atom carbocations in the bond retains one in the bond retains both electron electron Cl University of Slide CHEM 494, Spring 2010 18 Illinois at Chicago UIC Lecture 6: October 15 Radical Chain Mechanism Step Two Propagation vis H-Atom Abstraction alkyl hydrogen radical H abstraction H Cl H C CH3 C CH3 + HCl H H chlorine 7 valence radical electrons • Cl radical abstracts H atom from most substituted C atom • alkyl radical is an intermediate in the mechanism ˛ • alkyl radicals are stabilized by same factors that stabilize carbocations • note that radical is generated - propagation! University of Slide CHEM 494, Spring 2010 19 Illinois at Chicago UIC Lecture 6: October 15 Radical Chain Mechanism Step Three Propagation vis Cl-Atom Abstraction halogen H abstraction H Cl Cl C CH3 Cl C CH3 + Cl H H chlorine chlorine alkyl radical alkyl chloride molecule radical • alkyl radical abstract a halogen from a 2nd X2 molecule • chlorine radical product continues on in chain; starts the cycle over again by abstracting hydrogen from another alkane • radical chain mechanisms are faster than a stepwise mechanism which would require initiation in each step University of Slide CHEM 494, Spring 2010 20 Illinois at Chicago UIC Lecture 6: October 15 Complete Mechanism homolysis n o i Cl Cl Cl + Cl t a i light (hν) t i 7 valence n electrons I hydrogen H abstraction H Cl H C CH3 C CH3 + HCl n H H o i t 7 valence a electrons g a p o r halogen P H abstraction H Cl Cl C CH 3 Cl C CH3 + Cl H H University of Slide CHEM 494, Spring 2010 21 Illinois at Chicago UIC Lecture 6: October 15 Structure of Alkyl Radical Intermediates • radicals are high energy intermediates; 7 valence electrons; cannot be isolated • sp2-hybridized; contain one empty p- orbital; unpaired electron in the p- C H orbital; H C 3 H • approximately planar: three bonds to carbon are at ~120º angles from each other and ~90º to half-#lled p-orbital alkyl radicals can be stabilized by inductive effects and hyperconjugation; • stabilized by inductive effects and similar to carbocations hyperconjugation • Stability: 3º > 2º >> 1º > CH3 University of Slide CHEM 494, Spring 2010 22 Illinois at Chicago UIC Lecture 6: October 15 Stabilizing Effects on Alkyl Radicals • smallest inductive effect • largest inductive effect • no hyperconjugation • most hyperconjugation University of Slide CHEM 494, Spring 2010 23 Illinois at Chicago UIC Lecture 6: October 15 Bromination is More Selective Than Chlorination H H † Cl † ∆Ea (chlorination) Hammond Postulate H3C CH3 ‡ • chlorine radicals are higher in energy than bromine radicals = ∆Ea (bromination) H H ‡ • transition states in chlorination are earlier= Br H3C CH3 • look more like reactants = H H • less difference in TS energy = less selective = H3C CH2 • H • greater mixture † = early transition state structures ‡ = late transition state structures H3C CH3 • bromine radicals are lower in energy than ∆Ea (bromination) > ∆Ea (chlorination) chlorine radicals = Bromination is more selective. • transition states in bromination are later= Relative Rates (krel) of Halogenation • look more like products (radical interm.) = R3CH R2CH2 RCH3 • greater difference in TS energy = (tertiary, 3º) (secondary, 2º) (primary, 1º) more selective
Load more

Recommended publications
  • Electronic Structures and Spin Topologies of #-Picoliniumyl Radicals
    Subscriber access provided by UNIV OF MISSOURI COLUMBIA Article Electronic Structures and Spin Topologies of #-Picoliniumyl Radicals. A Study of the Homolysis of N-Methyl-#-picolinium and of Benzo-, Dibenzo-, and Naphthoannulated Analogs Rainer Glaser, Yongqiang Sui, Ujjal Sarkar, and Kent S. Gates J. Phys. Chem. A, 2008, 112 (21), 4800-4814 • DOI: 10.1021/jp8011987 • Publication Date (Web): 22 May 2008 Downloaded from http://pubs.acs.org on December 12, 2008 More About This Article Additional resources and features associated with this article are available within the HTML version: • Supporting Information • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article The Journal of Physical Chemistry A is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 4800 J. Phys. Chem. A 2008, 112, 4800–4814 Electronic Structures and Spin Topologies of γ-Picoliniumyl Radicals. A Study of the Homolysis of N-Methyl-γ-picolinium and of Benzo-, Dibenzo-, and Naphthoannulated Analogs Rainer Glaser,*,† Yongqiang Sui,† Ujjal Sarkar,† and Kent S. Gates*,†,‡ Departments of Chemistry and Biochemistry, UniVersity of Missouri-Columbia, Columbia, Missouri 65211 ReceiVed: February 9, 2008 Radicals resulting from one-electron reduction of (N-methylpyridinium-4-yl) methyl esters have been reported to yield (N-methylpyridinium-4-yl) methyl radical, or N-methyl-γ-picoliniumyl for short, by heterolytic cleavage of carboxylate. This new reaction could provide the foundation for a new structural class of bioreductively activated, hypoxia-selective antitumor agents. N-methyl-γ-picoliniumyl radicals are likely to damage DNA by way of H-abstraction and it is of paramount significance to assess their H-abstraction capabilities.
    [Show full text]
  • An Indicator of Triplet State Baird-Aromaticity
    inorganics Article The Silacyclobutene Ring: An Indicator of Triplet State Baird-Aromaticity Rabia Ayub 1,2, Kjell Jorner 1,2 ID and Henrik Ottosson 1,2,* 1 Department of Chemistry—BMC, Uppsala University, Box 576, SE-751 23 Uppsala, Sweden; [email protected] (R.A.); [email protected] (K.J.) 2 Department of Chemistry-Ångström Laboratory Uppsala University, Box 523, SE-751 20 Uppsala, Sweden * Correspondence: [email protected]; Tel.: +46-18-4717476 Received: 23 October 2017; Accepted: 11 December 2017; Published: 15 December 2017 Abstract: Baird’s rule tells that the electron counts for aromaticity and antiaromaticity in the first ππ* triplet and singlet excited states (T1 and S1) are opposite to those in the ground state (S0). Our hypothesis is that a silacyclobutene (SCB) ring fused with a [4n]annulene will remain closed in the T1 state so as to retain T1 aromaticity of the annulene while it will ring-open when fused to a [4n + 2]annulene in order to alleviate T1 antiaromaticity. This feature should allow the SCB ring to function as an indicator for triplet state aromaticity. Quantum chemical calculations of energy and (anti)aromaticity changes along the reaction paths in the T1 state support our hypothesis. The SCB ring should indicate T1 aromaticity of [4n]annulenes by being photoinert except when fused to cyclobutadiene, where it ring-opens due to ring-strain relief. Keywords: Baird’s rule; computational chemistry; excited state aromaticity; Photostability 1. Introduction Baird showed in 1972 that the rules for aromaticity and antiaromaticity of annulenes are reversed in the lowest ππ* triplet state (T1) when compared to Hückel’s rule for the electronic ground state (S0)[1–3].
    [Show full text]
  • Electron Ionization
    Chapter 6 Chapter 6 Electron Ionization I. Introduction ......................................................................................................317 II. Ionization Process............................................................................................317 III. Strategy for Data Interpretation......................................................................321 1. Assumptions 2. The Ionization Process IV. Types of Fragmentation Pathways.................................................................328 1. Sigma-Bond Cleavage 2. Homolytic or Radical-Site-Driven Cleavage 3. Heterolytic or Charge-Site-Driven Cleavage 4. Rearrangements A. Hydrogen-Shift Rearrangements B. Hydride-Shift Rearrangements V. Representative Fragmentations (Spectra) of Classes of Compounds.......... 344 1. Hydrocarbons A. Saturated Hydrocarbons 1) Straight-Chain Hydrocarbons 2) Branched Hydrocarbons 3) Cyclic Hydrocarbons B. Unsaturated C. Aromatic 2. Alkyl Halides 3. Oxygen-Containing Compounds A. Aliphatic Alcohols B. Aliphatic Ethers C. Aromatic Alcohols D. Cyclic Ethers E. Ketones and Aldehydes F. Aliphatic Acids and Esters G. Aromatic Acids and Esters 4. Nitrogen-Containing Compounds A. Aliphatic Amines B. Aromatic Compounds Containing Atoms of Nitrogen C. Heterocyclic Nitrogen-Containing Compounds D. Nitro Compounds E. Concluding Remarks on the Mass Spectra of Nitrogen-Containing Compounds 5. Multiple Heteroatoms or Heteroatoms and a Double Bond 6. Trimethylsilyl Derivative 7. Determining the Location of Double Bonds VI. Library
    [Show full text]
  • Mechanistic Approach to Thermal Production of New Materials from Asphaltenes of Castilla Crude Oil
    processes Article Mechanistic Approach to Thermal Production of New Materials from Asphaltenes of Castilla Crude Oil Natalia Afanasjeva 1, Andrea González-Córdoba 2,* and Manuel Palencia 1 1 Department of Chemistry, Faculty of Natural and Exact Science, Universidad del Valle, Cali 760020, Colombia; [email protected] (N.A.); [email protected] (M.P.) 2 Department of Chemical and Environmental Engineering, Faculty of Engineering, Universidad Nacional de Colombia, Bogotá 111321, Colombia * Correspondence: [email protected]; Tel.: +57-1-316-5000 (ext. 14322) Received: 16 August 2020; Accepted: 23 October 2020; Published: 12 December 2020 Abstract: Asphaltenes are compounds present in crude oils that influence their rheology, raising problems related to the extraction, transport, and refining. This work centered on the chemical and structural changes of the asphaltenes from the heavy Colombian Castilla crude oil during pyrolysis between 330 and 450 ◦C. Also, the development of new strategies to apply these macromolecules, and the possible use of the cracking products as a source of new materials were analyzed. The obtained products (coke, liquid, and gas) were collected and evaluated through the techniques of proton and carbon-13 nuclear magnetic resonance (1H and 13C NMR), elemental composition, Fourier-transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD), saturates, aromatics, resins, and asphaltenes (SARA) analysis, and gas chromatography–mass spectrometry (GC-MS). A comparison of the applied methods showed that the asphaltene molecules increased the average size of their aromatic sheets, lost their aliphatic chains, condensed their aromatic groups, and increased their degree of unsaturation during pyrolysis. In the liquid products were identified alkylbenzenes, n-alkanes C9–C30, and n-alkenes.
    [Show full text]
  • Developing a S Ystem to Study the Dynamics of the Heterolysis of Psubstituted Radicals in Terms of Magnetic Field Effects
    Developing a S ystem to Study the Dynamics of the Heterolysis of PSubstituted Radicals in terms of Magnetic Field Effects by Elaine K. Adams Submitted in partial fulfiiIlment of the requirements for the degree of Master of Science Dalhousie University Halifax, Nova Scotia September, 1998 @ Copyright by Elaine K. Adams, 1998 National hirary Bibliothèque nationale du Canada Acquisitions and Acquisiins et Biliograpfii Services seMces bibliographiques The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distribute or seli reproduire, prêter, distriiuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la forme de micro fi ch el^ de reproduction sur papier ou sur fonnat électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fkom it Ni la thése ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. Table of Contents List of Figures ........................................................................................ vi ... List of Tables ........................................................................................ xm 1.1 General Introduction .......................................................................
    [Show full text]
  • Coordinate Covalent C F B Bonding in Phenylborates and Latent Formation of Phenyl Anions from Phenylboronic Acid†
    J. Phys. Chem. A 2006, 110, 1295-1304 1295 Coordinate Covalent C f B Bonding in Phenylborates and Latent Formation of Phenyl Anions from Phenylboronic Acid† Rainer Glaser* and Nathan Knotts Department of Chemistry, UniVersity of MissourisColumbia, Columbia, Missouri 65211 ReceiVed: July 4, 2005; In Final Form: August 8, 2005 The results are reported of a theoretical study of the addition of small nucleophiles Nu- (HO-,F-)to - phenylboronic acid Ph-B(OH)2 and of the stability of the resulting complexes [Ph-B(OH)2Nu] with regard - - - - - to Ph-B heterolysis [Ph-B(OH)2Nu] f Ph + B(OH)2Nu as well as Nu /Ph substitution [Ph-B(OH)2Nu] - - - + Nu f Ph + [B(OH)2Nu2] . These reactions are of fundamental importance for the Suzuki-Miyaura cross-coupling reaction and many other processes in chemistry and biology that involve phenylboronic acids. The species were characterized by potential energy surface analysis (B3LYP/6-31+G*), examined by electronic structure analysis (B3LYP/6-311++G**), and reaction energies (CCSD/6-311++G**) and solvation energies - (PCM and IPCM, B3LYP/6-311++G**) were determined. It is shown that Ph-B bonding in [Ph-B(OH)2Nu] is coordinate covalent and rather weak (<50 kcal‚mol-1). The coordinate covalent bonding is large enough to inhibit unimolecular dissociation and bimolecular nucleophile-assisted phenyl anion liberation is slowed greatly by the negative charge on the borate’s periphery. The latter is the major reason for the extraordinary differences in the kinetic stabilities of diazonium ions and borates in nucleophilic substitution reactions despite their rather similar coordinate covalent bond strengths.
    [Show full text]
  • Hydrogen Peroxide As a Hydride Donor and Reductant Under Biologically Relevant Conditions† Cite This: Chem
    Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Hydrogen peroxide as a hydride donor and reductant under biologically relevant conditions† Cite this: Chem. Sci.,2019,10,2025 ab d c All publication charges for this article Yamin Htet, Zhuomin Lu, Sunia A. Trauger have been paid for by the Royal Society and Andrew G. Tennyson *def of Chemistry Some ruthenium–hydride complexes react with O2 to yield H2O2, therefore the principle of microscopic À reversibility dictates that the reverse reaction is also possible, that H2O2 could transfer an H to a Ru complex. Mechanistic evidence is presented, using the Ru-catalyzed ABTScÀ reduction reaction as a probe, which suggests that a Ru–H intermediate is formed via deinsertion of O2 from H2O2 following Received 5th December 2018 À coordination to Ru. This demonstration that H O can function as an H donor and reductant under Accepted 7th December 2018 2 2 biologically-relevant conditions provides the proof-of-concept that H2O2 may function as a reductant in DOI: 10.1039/c8sc05418e living systems, ranging from metalloenzyme-catalyzed reactions to cellular redox homeostasis, and that À rsc.li/chemical-science H2O2 may be viable as an environmentally-friendly reductant and H source in green catalysis. Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction bond and be subsequently released as H2O2 (Scheme 1A, red arrows).12,13 The principle of microscopic reversibility14 there- Hydrogen peroxide and its descendant reactive oxygen species fore dictates that it is mechanistically equivalent for H2O2 to (ROS) have historically been viewed in biological systems nearly react with a Ru complex and be subsequently released as O2 exclusively as oxidants that damage essential biomolecules,1–3 with concomitant formation of a Ru–H intermediate (Scheme but recent reports have shown that H2O2 can also perform 1A, blue arrows).
    [Show full text]
  • Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: the Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction
    Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications Chemistry, Department of 10-23-2014 Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction Matthew Flister Marquette University, [email protected] Qadir K. Timerghazin Marquette University, [email protected] Follow this and additional works at: https://epublications.marquette.edu/chem_fac Part of the Chemistry Commons Recommended Citation Flister, Matthew and Timerghazin, Qadir K., "Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction" (2014). Chemistry Faculty Research and Publications. 360. https://epublications.marquette.edu/chem_fac/360 Marquette University e-Publications@Marquette Chemistry Faculty Research and Publications/College of Arts and Sciences This paper is NOT THE PUBLISHED VERSION; but the author’s final, peer-reviewed manuscript. The published version may be accessed by following the link in the citation below. Journal of Physical Chemistry : A, Vol. 18, No. 42 (October 23, 2014): 9914–9924. DOI. This article is © American Chemical Society Publications and permission has been granted for this version to appear in e-Publications@Marquette. American Chemical Society Publications does not grant permission for this article to be further copied/distributed or hosted elsewhere without the express permission from American Chemical Society Publications. Structure, Stability, and Substituent Effects in Aromatic S-Nitrosothiols: The Crucial Effect of a Cascading Negative Hyperconjugation/Conjugation Interaction Matthew Flister Department of Chemistry, Marquette University, Milwaukee, Wisconsin Qadir K. Timerghazin Department of Chemistry, Marquette University, Milwaukee, Wisconsin Abstract Aromatic S-nitrosothiols (RSNOs) are of significant interest as potential donors of nitric oxide and related biologically active molecules.
    [Show full text]
  • Development of a High-Density Initiation Mechanism for Supercritical Nitromethane Decomposition
    The Pennsylvania State University The Graduate School DEVELOPMENT OF A HIGH-DENSITY INITIATION MECHANISM FOR SUPERCRITICAL NITROMETHANE DECOMPOSITION A Thesis in Mechanical Engineering by Christopher N. Burke © 2020 Christopher N. Burke Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science August 2020 The thesis of Christopher N. Burke was reviewed and approved by the following: Richard A. Yetter Professor of Mechanical Engineering Thesis Co-Advisor Adrianus C. van Duin Professor of Mechanical Engineering Thesis Co-Advisor Jacqueline A. O’Connor Professor of Mechanical Engineering Karen Thole Professor of Mechanical Engineering Mechanical Engineering Department Head ii Abstract: This thesis outlines the bottom-up development of a high pressure, high- density initiation mechanism for nitromethane decomposition. Using reactive molecular dynamics (ReaxFF), a hydrogen-abstraction initiation mechanism for nitromethane decomposition that occurs at initial supercritical densities of 0.83 grams per cubic centimeter was investigated and a mechanism was constructed as an addendum for existing mechanisms. The reactions in this mechanism were examined and the pathways leading from the new initiation set into existing mechanism are discussed, with ab-initio/DFT level data to support them, as well as a survey of other combustion mechanisms containing analogous reactions. C2 carbon chemistry and soot formation pathways were also included to develop a complete high-pressure mechanism to compare to the experimental results of Derk. C2 chemistry, soot chemistry, and the hydrogen-abstraction initiation mechanism were appended to the baseline mechanism used by Boyer and analyzed in Chemkin as a temporal, ideal gas decomposition. The analysis of these results includes a comprehensive discussion of the observed chemistry and the implications thereof.
    [Show full text]
  • Understanding Metal-Metal Bonds in Heterobimetallic Complexes and Their Use As Catalysts for Dinitrogen Conversion
    Understanding Metal-Metal Bonds in Heterobimetallic Complexes and Their Use as Catalysts for Dinitrogen Conversion A DISSERTATION SUBMITTED TO THE FACULTY OF THE UNIVERSITY OF MINNESOTA BY Laura J. Clouston IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Connie C. Lu, Advisor July 2016 © Laura J Clouston 2016 Acknowledgments I am grateful to obtain my degree from the Chemistry Department at the University of Minnesota, were I could not be surrounded by better people. I was lucky to be a part of the Lu group, where I could always find someone to talk science or have a good laugh. I would like to thank Connie for welcoming me into the group and providing me with numerous opportunities to grow as a scientist. Thanks to the rest of the Lu group, past and present, you have all taught me something valuable that I will keep with me. Thanks to Deanna for guiding me through my first two years, and to Steve, Reed and Ryan for always keeping my expectations high. Thanks to Dave, the second year crew- Matt, Bianca, JT and Sai, and Azim for keeping the lab to be a fun place to spend the majority of your time. A special thanks to the Gagliardi group for a great collaboration, especially Varinia, who has calculated almost everything I have made or wanted to make, I have truly enjoyed working together. I am also thankful for the groups in the department that I have worked closely with, the Tonks, Tolman, Que, Ellis and Hoye groups, who have provided a wealth of advice, resources and chemicals throughout my graduate work.
    [Show full text]
  • View of Bicyclic Cobalt Cation 42
    University of Alberta Cobalt(III)-Mediated Cycloalkenyl-Alkyne Cycloaddition and Cycloexpansion Reactions by Bryan Chi Kit Chan A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy Chemistry ©Bryan Chi Kit Chan Spring 2010 Edmonton, Alberta Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission. Examining Committee Jeffrey M. Stryker, Chemistry, University of Alberta Martin Cowie, Chemistry, University of Alberta Jillian M. Buriak, Chemistry, University of Alberta Frederick G. West, Chemistry, University of Alberta William C. McCaffrey, Chemical Engineering, University of Alberta Lisa Rosenberg, Chemistry, University of Victoria Abstract A comprehensive investigation of cycloalkenyl-alkyne coupling reactions mediated by cobalt(III) templates is presented. The in situ derived cationic η3- cyclohexenyl complexes of cobalt(III) react with some terminal alkynes to afford either η1,η4-bicyclo[4.3.1]decadienyl or η2,η3-vinylcyclohexenyl products, depending on the type and concentration of the alkyne. The mechanism for this cyclohexenyl-alkyne cycloaddition reaction is consistent with the previously reported cobalt-mediated [3 + 2 + 2] allyl-alkyne coupling reaction.
    [Show full text]
  • Photoremovable Protecting Groups
    1348_C69.fm Page 1 Monday, October 13, 2003 3:22 PM 69 Photoremovable Protecting Groups 69.1 Introduction ..................................................................... 69-1 69.2 Historical Review.............................................................. 69-2 o-Nitrobenzyl • Benzoin • Phenacyl • Coumaryl and Arylmethyl 69.3 Carboxylic Acids............................................................. 69-17 o-Nitrobenzyl • Coumaryl • Phenacyl • Benzoin • Other Richard S. Givens 69.4 Phosphates and Phosphites ........................................... 69-23 o-Nitrobenzyl • Coumaryl • Phenacyl • Benzoin University of Kansas 69.5 Sulfates and Other Acids................................................ 69-26 Peter G. Conrad, II 69.6 Alcohols, Thiols, and N-Oxides .................................... 69-27 University of Kansas o-Nitrobenzyl • Thiopixyl and Coumaryl • Benzoin • Other Abraham L. Yousef 69.7 Phenols and Other Weak Acids..................................... 69-36 o-Nitrobenzyl • Benzoin University of Kansas 69.8 Amines ............................................................................ 69-37 Jong-Ill Lee o-Nitrobenzyl • Benzoin Derivatives • Arylsulfonamides University of Kansas 69.9 Conclusion...................................................................... 69-40 69.1 Introduction Photoremovable protecting groups are enjoying a resurgence of interest since their introduction by Kaplan1a and Engels1b in the late 1970s. A review of published work since 19932 is timely and will provide information about
    [Show full text]