DOCSLIB.ORG

Developing a S Ystem to Study the Dynamics of the Heterolysis of Psubstituted Radicals in Terms of Magnetic Field Effects

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read 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 ........................................................................ -1 1.2 Introduction to the Radical Pair Model .....................................................2 1.2.1 GeneraI MiceUar Characteristics....................................................... 4 1.3 Observation of Magnetic Field Effects ..................................................... 6 1-4 Magne tic Field Effec ts on PHeterolysis Reac tions .................................... 12 1-5 Scope of Thesis................ ... .......................................... .. ......... 15 Chapter 2 Heterolytic Cleavage for p-Substituted Radicals ................. 16 2.1 General Introduction ....................................................................... 16 2.2 Laser Photolysis of 2-Chloro- 1-(4-methoxyphenyl)ethyl acetate..................... 18 2.3 Laser Photolysis of 2-Chloro- 1-(4-methoxypheny1)propyl acetate.................. -21 2.4 Laser Photolysis of 2-Bromo- 1-(4-methoxypheny1)ethyl acetate.................... -23 2.5 Laser Photolysis of 2-Bromo- 1-(4-methoxypheny1)propyl acetate ................... 25 2.6 Discussion ...................................................................................27 Chapter 3 Reactivity of Radical Cations with Radicals ...................... 33 3- 1 GeneraI Introduction ....................................................................... 33 3.2 Laser Photolysis of Anethole in Acetonitrile ............................................ 35 3.2.1 Laser Photolysis with Benzyl bromide ............................................. 36 3.2.2 Laser Photolysis with 3-Cyanobenzyl brornide ................................... 42 3.2.3 Laser Photolysis with Diphenylmethyl chloride................................... 46 3.2.4 Identification of the Transient at 345 nm ........................................... 49 3.3 Laser Photolysis of Anethole in SDS .................................................... 56 3.3.1 Laser Photolysis with Benzyl bromide ............................................. 57 3.3.2 Laser Photolysis with 3-Cyanobenzyl bromide ................................... 61 3.3.3 Laser Photolysis with Toluene and 3-Cyanotoluene.............................. 64 3.4 Laser Photolysis of Anethole in CTAB .................................................. 69 3.4.1 Laser Photolysis with Benzyl bromide ............................................ -70 3.5 Laser Photolysis of p-Methoxystyrene in Acetonibile ................................. 72 3.5.1 Laser Photolysis with Benzyl bromide ............................................. 74 3.5.2 Laser Photolysis with 3-Cyanobenzyl bromide ................................... 78 3.5.3 2-Bromo- 1-(4-meth0xyphenyl)ethyl Radical Formation ......................... 80 3.6 Irradiation of ~Methoxystyrenein SDS................................................. 83 3.6.1 Laser Photolysis with Benzyl bromide ............................................. 84 3.6.2 Laser Photolysis with 3-Cyanobenzyl bromide ................................... 88 3.6.3 Laser Photolysis with Toluene and 3-Cyanotoluene .............................. 91 3.7 Irradiation of p-Methoxystyrene in CTAB .............................................. 94 3.8 Discussion................................................................................. 97 3.8.1 Homogeneous media: Acetonitrile .................................................. 97 3.8.2 Heterogeneous medi a.. .............................................................. IO1 Chapter 4 Preliminary Work in Radical Pair Generation .................. 105 4.1 General Introduction ..................................................................... -105 4.2 Addition of -CH2Br and -CH20COPh to Dibenzylketone.......................... -106 4.3 Addition of Formaldehyde to Dibenzyketone ......................................... 107 4.4 Preparation of 1,3~bis(4.methoxyphenyl)~2~propanone.............................. IO8 4.4.1 Addition of -CH2Br and -CH20COPh ........................................... 109 4.4.2 Addition of Formaldehyde .......................................................... 109 4.5 Laser Expe~hents......................................................................... Il0 4.5.1 Magnetic Field Trial ................................................................. 111 4.6 Future Work ............................................................................... 114 Chapter 5 Experimental ........................... .... ..... ............ 115 5.1 Materials .................................................................................... 115 5.2 General Instmtmention ................................................................... 115 5.3 Laser Flash Photolysis.................................................................... 116 5.3.1 Equipment ........................................................................... -116 5.3.2 Data Processing ...................................................................... 117 5.4 Sample Preparation........................................................................ 117 5.4.1 p-Heterolysis studies ................................................................ 117 5.4.2 Photoionkation studies .............................................................. 118 5.5 Laser Photolysis with an Applied Magnetic Field ..................................... 120 5.5.1 Sample Preparation .................................................................. 120 5.5.2 Apparatus ............................................................................ -121 5.6 Syuthetic Procedures ...................................................................... 121 References .......................................................................................... 126 List of Fimes Figure 2- 1. Transient absorption spectnim of 2-chloro- 1-(4-methoxypheny1)e thyl acetate in nitrogen-saturated 0.1 M SDS recorded 76 (a), 128 (O) 224 (a),and 368 (Ci) ns after the laser pulse. Inset shows the tirne-resolved growth at 370 nrn under nitrogen (a) and oxygen-saturated (O)conditions. ................................................................. 20 Figure 2-2. Transient absorption spectrum of 2chloro- L -(4-methoxypheny1)ethyl acetate in nitrogen-saturated 0.05 M CTAB recorded 2 10 ns (a),540 ns (O), 920 ns (a), and 1.86 ps ((O) after the laser pulse. Inset shows the tirne-resolved growth at 370 nm under nitrogen (8)and oxygen-saturateci (O) conditions.. ........................................... -20 Figure 2-3. Transient absorption spectrum of 2cbioro- 1-(4-methoxypheny1)propyl acetate in nitrogen-saturated 0.1 M SDS recorded 70 (@), 148 (O), 232 (m), and 564 (0)ns afier the laser pulse. Inset shows. the tirne-resolved growth at 390 nrn under nitrogen (a) and oxygen-saturated (O) conditions. ................................................................. 22 Figure 24. Transient absorption spectmm 2chloro- 1-(4-methoxypheny1)propyl acetate in nitrogen-saturated 0.05 M CT'AB recorded 208 ns (a), 552 ns (O), and 1.29 ps (i)after the laser pulse. Inset shows. the the-resolved growth at 390 nrn under nitrogen (a) and oxygen-saturated (O) conditions. ................................................................. 22 Figure 2-5. Transient absorption spectnim of 2-bromo- 1-(4-methoxypheny1)ethyl acetate in nitrogen-saturated 0.1 M SDS recorded 120 (a), 308 (O), and 548 (i)ns after the laser pulse. Inset shows decay trace at 370 nm under N2 (a) and 02(O) conditions.. .........24 Figure 2-6. Transient absorption spectrum of 2-bromo- 1-(4-methoxypheny1)ethyl acetate in nitrogen-saturated 0.05 M CTAB recorded 130 (a),300 (O), and 670 (i) ns after the laser pulse. Inset shows decay trace at 350 nm under N;! (e)and 02 (0)conditions.. ... 24 Figure 2-7. Transient absorption spectrum of 2-bromo- 1-(4-methoxypheny1)propyl acetate in nitrogen-saturated 0.1 M SDS recorded 60 (a), 192 (O), 408 (W), and 640 (0)ns after the laser pulse. Inset shows the decay trace rnonitored at 390 nm under nitrogen (a) and oxygen-saturated
Load more

Recommended publications
  • 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]
  • 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]
  • 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]
  • Information to Users
    INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms international A Bell & Howell Information Company 300 North ZeebRoad Ann Arbor Ml 48106-1346 USA 313/761-4700 800 521-0600 Order Number 9427071 The chemistry of polycyclic and spirocyclic compounds Branan, Bruce Monroe, Ph.D. The Ohio State University, 1994 UMI 300 N.ZeebRd. Ann Arbor, MI 48106 THE CHEMISTRY OF POLYCYCLIC AND SPIROCYCLIC COMPOUNDS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Bruce Monroe Branan ***** The Ohio State University 1994 Dissertation Committee: Approved by Professor Leo A.
    [Show full text]
  • Organic Chemistry 1 Lecture 8
    CHEM 232 University of Illinois Organic Chemistry I at Chicago UIC Organic Chemistry 1 Lecture 8 Instructor: Prof. Duncan Wardrop Time/Day: T & R, 12:30-1:45 p.m. February 04, 2010 1 Self Test Question Which of the following transformations is unlikely to generate the product indicated? OH HCl Cl a. 25 ºC primary alcohols HCl A. a. and HCl are insufficiently x b. OH 25 ºC Cl reactive B. b. SOCl2 O O c. OH Cl C. c. K2CO3 Cl D. d. d. Cl2 hν University of Slide CHEM 232, Spring 2010 2 Illinois at Chicago UIC Lecture 8: February 4 2 Compound “b.” is a primary alcohol, which are insufciently reactive to undergo reaction with hydrogen chloride. Primary alcohols do, however, react with thionyl chloride (SOCl2) to form chlorides and so the transformation shown in “c” will proceed successfully Compound “a” is tertiary alcohol and consequently reacts with HCl. Substitution Reaction hydroxyl group halide R O H + H X R X + H O H alcohol hydrogen alkyl water halide halide Hydroxyl group is being substituted (replaced with) a halide University of Slide CHEM 232, Spring 2010 3 Illinois at Chicago UIC Lecture 8: February 4 3 CHEM 232 University of Illinois Organic Chemistry I at Chicago UIC Mechanisms of Substitution Reactions Sections: 4.8-4.11 4 Substitution: How Does it Happen? break bond break bond make bond make bond R O H + H X R X + H O H alcohol hydrogen alkyl halide water halide mechanism: a generally accepted series of elementary steps that show the order of bond breaking and bond making elementary step: a bond making and/or bond breaking step
    [Show full text]
  • Covalent, Ionic, and Charge-Shift Bonds Sason Shaik, David Danovich, Benoît Braïda, Wei Wu, Philippe C
    New Landscape of Electron-Pair Bonding: Covalent, Ionic, and Charge-Shift Bonds Sason Shaik, David Danovich, Benoît Braïda, Wei Wu, Philippe C. Hiberty To cite this version: Sason Shaik, David Danovich, Benoît Braïda, Wei Wu, Philippe C. Hiberty. New Landscape of Electron-Pair Bonding: Covalent, Ionic, and Charge-Shift Bonds. Mingos, D. Michael P. The Chemical Bond II, 170, Springer International Publishing, pp.169–211, 2015, 978-3-319-33520-9 978-3-319-33522- 3. hal-01627700 HAL Id: hal-01627700 https://hal.archives-ouvertes.fr/hal-01627700 Submitted on 10 Nov 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. New Landscape of Electron-Pair Bonding: Covalent, Ionic, and Charge-Shift Bonds Sason Shaik, David Danovich, Benoit Braida, Wei Wu, and Philippe C. Hiberty Abstract We discuss here the modern valence bond (VB) description of the electron-pair bond vis-a-vis the Lewis–Pauling model and show that along the two classical families of covalent and ionic bonds, there exists a family of charge-shift bonds (CSBs) in which the “resonance fluctuation” of the electron- pair density plays a dominant role. A bridge is created between the VB description of bonding and three other approaches to the problem: the electron localization function (ELF), atoms-in-molecules (AIM), and molecular orbital (MO)-based theories.
    [Show full text]
  • LA.2.1 Reaction Mechanisms
    LA.2.1 Reaction Mechanisms Curly Arrows In a chemical reaction bonds are broken and new bonds made. A reaction mechanism describes the steps involved and makes it clear how these bonds are formed and broken. The slowest step in the reaction is known as the RATE DETERMINING STEP. Curly arrows represent the movement of electrons. A FULL arrow represents an electron pair (see Figure 1) whereas a HALF arrow represents a single electron (see Figure 2) which is traditionally reserved for radical chemistry. H+ + Cl- 2Cl Figure 1 The heterolysis of HCl Figure 2 The homolysis of Cl2 When a bond is broken and both electrons go to the same atom (represented by a full arrow), this is called HETEROLYTIC FISSION. When a bond is broken and the bonding electrons are evenly split (represented by a half arrow), this is called HOMOLYTIC FISSION. Nucleophiles Electrophiles Definition: Electron pair DONOR. Nucleophiles Definition: Electron pair ACCEPTOR. are also known as Lewis bases. Electrophiles are also known as Lewis acids. Compounds which act as nucleophiles have a Compounds which act as electrophiles are high electron density electron deficient Common nucleophiles: Common electrophiles: - - - + + + Anions CN, OH, Cl Cations H , CH3 , NO2 Π Bonds Alkenes, Alkynes, Polar molecules Haloalkanes, Ketones, (electrophilic site at δ+) Aromatic compounds e.g benzene Alcohols Atoms with Lone Amines, Ketones, Pairs Electron movement always goes from the nucleophile to the electrophile: Water Electrophilic Addition to Alkenes (Bromination) A classic test for alkenes is the addition of bromine (Br2) as the presence of an alkene such as ethene, changes the brown bromine to colourless.
    [Show full text]
  • Secondary Coordination Sphere Contributions to Primary Sphere Structure, Bonding and Reactivity
    Secondary coordination sphere contributions to primary sphere structure, bonding and reactivity by Cameron M. Moore A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) in The University of Michigan 2015 Doctoral Committee: Assistant Professor Nathaniel K. Szymczak, chair Professor Vincent L. Pecoraro Professor Stephen W. Ragsdale Professor Melanie S. Sanford © Cameron M. Moore 2015 Dedication For my family ii Acknowledgments I would first like to thank Professor Nate Szymczak for mentoring me over the past five years. I feel fortunate to have been one of the first students in his group and help build the lab from the ground up. Nate has given me tremendous amounts of freedom during my graduate career to explore concepts and pursue wild ideas. He has also always had an open door while I’ve been in the group. I wouldn’t be able to count the number of times I’ve come to his office in a panic and he’s been there to help me keep my cool. I’ve learned how to write, think critically and practice good science from Nate, and for that I am very thankful. I’d like to thank the members of my dissertation committee, both past and present: Prof. Melanie Sanford, Prof. Steve Ragsdale, Prof. Vince Pecoraro and Prof. Mi Hee Lim. During our meetings, I have very much appreciated your input and advice. I have valued the different perspectives you have all provided during these times and thank you for helping me to understand science in a more broad sense.
    [Show full text]
  • The Investigation of Iron(II) Complexes and Their Catalytic Applications
    University of Missouri, St. Louis IRL @ UMSL Dissertations UMSL Graduate Works 5-17-2013 The nI vestigation of Iron(II) Complexes and Their Catalytic Applications Matthew oJ seph Lenze University of Missouri-St. Louis, [email protected] Follow this and additional works at: https://irl.umsl.edu/dissertation Part of the Chemistry Commons Recommended Citation Lenze, Matthew Joseph, "The nI vestigation of Iron(II) Complexes and Their aC talytic Applications" (2013). Dissertations. 308. https://irl.umsl.edu/dissertation/308 This Dissertation is brought to you for free and open access by the UMSL Graduate Works at IRL @ UMSL. It has been accepted for inclusion in Dissertations by an authorized administrator of IRL @ UMSL. For more information, please contact [email protected]. The Investigation of Iron(II) Complexes and Their Catalytic Applications Matthew J. Lenze M.S. in Chemistry, University of Missouri-St. Louis, 2010 B.S. in Chemistry, University of Missouri-St. Louis, 2008 A Thesis submitted to the Graduate School at the University of Missouri - St. Louis in partial fulfillment of the requirements for the degree Doctor of Philosophy in Chemsitry May 2013 Advisory Committee Eike Bauer, Ph.D. Chairperson Christopher Spilling, Ph. D. Wesley Harris, Ph. D. Keith Stine. Ph. D. Table of Contents LIST OF ABBREVIATIONS ............................................................................ 5 ABSTRACT ......................................................................................................... 6 CHAPTER 1 Introduction ................................................................................
    [Show full text]
  • Computational Studies of Noncovalent Interactions in Ligand-Gated Ion Channels - and - Synthesis and Characterization of Red and Near Infrared Cyanine Dyes
    Computational studies of noncovalent interactions in ligand-gated ion channels - and - Synthesis and characterization of red and near infrared cyanine dyes Thesis by Matthew Robert Davis In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2018 (Defended 10 August, 2017) ii 2017 Matthew Robert Davis ORCID: 0000-0002-6374-4555 iii Acknowledgements I have been immeasurably fortunate to have not only spent five years performing state-of-the-art basic research, but to have stumbled into many valuable relationships, friendships, and partnerships that have infused my life with happiness and meaning. There are many individuals that have made my experience at Caltech what it is today, but several deserve special mention; Dennis Dougherty, for being an excellent mentor and teacher. From Dennis I have learned the value of precise experimental design, the guiding principles of physical organic chemistry, and a healthy respect for effective pedagogy. He has given me the freedom to investigate a huge variety of different problems. This is reflected in my thesis: I have had the opportunity to study computational chemistry, ion channel electrophysiology, and organic synthesis of dye molecules. Not many advisors would allow such a broad focus, and I feel that it has allowed me to reach my potential as a graduate student. The chance to work closely on some of the computational work described in this thesis has been a dream come true. Perhaps most importantly, however, Dennis has imparted to our group the importance of a healthy work-life balance. I admire his relationship with Ellen, his knowledge of current events, and his Dodger fandom.
    [Show full text]
  • Role of Phoh and Tyrosine in Selective Oxidation of Hydrocarbons
    catalysts Article Role of PhOH and Tyrosine in Selective Oxidation of Hydrocarbons Ludmila Matienko * , Vladimir Binyukov † , Elena Mil and Alexander Goloshchapov Emanuel Institute of Biochemical Physics, Russian Academy of Science, 4 Kosygin Street, 119334 Moscow, Russia; [email protected] (V.B.); [email protected] (E.M.); [email protected] (A.G.) * Correspondence: [email protected] or [email protected] † Deceased. Abstract: Earlier, we established that nickel or iron heteroligand complexes, which include PhOH (nickel complexes) or tyrosine residue (nickel or iron complexes), are not only hydrocarbon oxidation catalysts (in the case of PhOH), but also simulate the active centers of enzymes (PhOH, tyrosine). The AFM method established the self-organization of nickel or iron heteroligand complexes, which included tyrosine residue or PhOH, into supramolecular structures on a modified silicon surface. Supramolecular structures were formed as a result of H-bonds and other non-covalent intermolecular interactions and, to a certain extent, reflected the structures involved in the mechanisms of reactions of homogeneous and enzymatic catalysis. Using the AFM method, we obtained evidence at the model level in favor of the involvement of the tyrosine fragment as one of the possible regulatory factors in the functioning of Ni(Fe)ARD dioxygenases or monooxygenases of the family of cytochrome P450. The principles of actions of these oxygenases were used to create highly efficient catalytic systems for the oxidation of hydrocarbons. Keywords: AFM; self-organization; PhOH; Tyr fragment; Ni(or Fe)-acac complexes; nanostructures; Citation: Matienko, L.; Binyukov, V.; Ni(Fe)ARD dioxygenases; cytochrome P450 monooxygenases; H-bonds; hemin; L-histidine; L-tyrosine Mil, E.; Goloshchapov, A.
    [Show full text]