DOCSLIB.ORG

Information to Users

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read 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. Paquette Professor Viresh H. Rawal Adviser Professor Harold Shechter Department of Chemistry For the Glory of My Lord and Savior, Jesus Christ. Proverbs 9:10 A CKNO WLEDG EMENTS This work would not exist without the assistance of numerous people, and it is a pleasure to begin by expressing my sincere appreciation to Professor Paquette for his guidance, support, and understanding throughout my stay in Columbus, and for the hard work that he always demanded, as well as provided. I thank Professor Rawal and Professor Shechter for serving on my Dissertation Committee, and Dr. Kurt Loening for assistance in naming the many compounds included in this document. Special thank-you is also given to Donna Rothe for her patience and endless smiles while going out of her way to help, and to Dr. Kevin Daniels for his generous assistance the numerous times I required aid with the computer. I am indebted to the many members of the Paquette Research Group both past and present, for their valuable chemical insights and assistance. I am grateful to Peter and Betsy Martindale and family, and Living Water Church for providing me with family and friends away from the laboratory. To my Mother and Father, and to my brother and sisters, a thank-you does not seem large enough, for their love and support is always there to depend on. Any goal I achieve must be shared by them. Furthermore, I am particularly grateful to Professor J.C. Barborak and Professor R.L. Miller at UNCG for their friendship and guidance during my undergraduate and graduate years. Finally, I thank my wife Laura, for the never ending love and support that she gives her husband. VITA May 28, 1967 .................................................... Bom, Winston-Salem, NC May 14, 1989 .................................................... Bachelor of Science University of NC at Greensboro Greensboro, North Carolina September, 1989-June, 1990.......................... Graduate Teaching Associate The Ohio State University June, 1990-December, 1992 ........................... Graduate Research Associate The Ohio State University January, 1993-December 1993 ...................... Graduate Fellow The Ohio State University PUBLICATIONS Paquette, L.A.; Branan, B.M.; Rogers, R.D. Tetrahedron 1992, 48, 297-306. Branan, B.M.; Paquette, L.A.; Hrovat, D.A.; Borden, W.T. J. Am. Chem. Soc. 1 99 2,114, 774-776. Paquette, L.A.; Dullweber, U.; Branan, B.M. Heterocycles 1994,37, 187-191. Paquette, L.A.; Branan, B.M.; Friedrich, D.; Edmondson, S.D.; Rogers, R.D. J. Am. Chem. Soc. 1994,116, 506-513. FIELD OF STUDY MAJOR HELD: Chemistry Studies in Organic Chemistry iv TABLE OF CONTENTS DEDICATION............................................................................................ ii ACKNOWLEDGMENTS............................................................................................... lii VITA.................................................................................................................................. iv LIST OF TABLES............................................................................................................ viii LIST OF FIGURES.......................................................................................................... x LIST OF SCHEMES........................................................................................................ xiii CHAPTER PAGE I. STUDIES TOWARD THE SYNTHESIS OF PENTACYCLO- [7.2.1.04’11.06'9.!)6’ , 0 ]DODECA-1,4-DIENE: A BIS-ANNELATED SEMIBULL VALENE A. Introduction ............................................................................ 1 B. Results................................................................................... 7 C. Discussion ............................................................................... 13 II. GENERATION AND CHEMICAL TRAPPING OF A BIS(ETHANO) DERIVATIVE OF TRICYCLO[3.3.0.03 7 ]OCT-l(5)-ENE: THE CONSUMMATE MEMBER OF A SERIES OF PYRAMIDALIZED ALKENES A. Introduction.......................................................................... 15 B. Results and Discussion ....................................................... 16 III. PROGRESS TOWARDS THE SYNTHESIS OF TRICYCLO[4.4.1 04*11 ] UNDECA-1,3,5,7,9-PENTAENE VIA BROMINATION- DEHYDROBROMINATION METHODOLOGY A. Introduction .......................................................................... 22 B. Results................................................................................... 24 C. Discussion ............................................................................. 31 IV. ANALYSIS OF THE CONFORMATIONAL NATURE, RESOLVABILITY, AND THERMAL RACEMIZATION OF HETERO-2,3-DISPIRO CYCLOHEX ANONES A. Introduction ......................................................................... 34 B. Results..................................................................................... 36 1. Synthetic Considerations ........................................ 36 2. Solid-State Structural Studies ................................. 38 3. Solution Conformational Studies .......................... 39 4. Assessment of the Relative Stabilities by Molecular Mechanics Calculations ................ 45 5. Acid-Catalyzed Syn/Anti Equilibration Studies....................................................................... 47 6 . Resolution of 72, 81, and 8 6 . Racemization under Acidic Conditions ............... 48 C. Discussion .............................................................................. 50 1. The 2-Heteroatom ketone Effect ........................... 50 2. The Gauche Effect of Vicinal Polar Bonds on Six-Membered Rings ........................................ 52 3. Counterbalancing of Electronic and Steric Interactions in Hetero 2,3-Dispiro Cyclohexanones ....................................................... 53 4. Heteroatom Control of Racemization at Two Vicinal Quaternary Carbons .................................. 54 V. HETEROATOMIC EFFECTS ON THE ACID-CATALYZED REARRANGEMENTS OF DISPIRO[4.0.4.4]TETRADECA- 11,13-DIENES A. Introduction ........................................................................... 56 B. Results..................................................................................... 57 1. Preparation of the Spirocyclic Dienes .................. 57 2. Acid Catalyzed Rearrangements ........................... 62 3. Selected Reactions of the [4.4.4]- Propelladienes ......................................................... 67 C. Discussion .............................................................................. 69 VI. INVESTIGATION OF HETEROATOM INFLUENCES ON THE DIELS-ALDER FACIAL SELECTIVITY OF DISPIRO[4.0.4.4]- TETR ADECA-11,13-DIENES A. Introduction ........................................................................... 72 B. Preparation of Starting Materials ....................................... 75 C. Results..................................................................................... 76 1. Cycloadditions .......................................................... 76 a. Diene 105 ...................................................... 76 b. Diene 102 ..................................................... 79 c. Diene 117 ...................................................... 81 d. Diene 155 ..................................................... 82 e. Diene 111 ...................................................... 83 f. Diene 114 ...................................................... 85 D. Discussion .............................................................................. 90 EXPERIMENTAL.............................................................................................................
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]
  • 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]
  • Xarox University Microfilms
    INFORMATION TO USERS Thil material was produced from a microfilm copy of the original documant. While the moat advanced technological meant to photograph and reproduce this documant have been used, the quality is heavily dependant upon the quality of the original submitted. The following explanation o f techniques is provided to help you understand markings or patterns which m ay appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Misting Page(s)". If it was possible to obtain the misting page(s) or section, th a y era spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pagae to insure you complete continuity. 2. Whan an image on th e film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus causa a blurred image. You will find a good image of the pnga in the adjacent frame. 3. Whan a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It ie customary to begin photoing at the upper left hand comer of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row end continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation.
    [Show full text]
  • 37Th Rocky Mountain Conference on Analytical Chemistry
    Rocky Mountain Conference on Magnetic Resonance Volume 37 37th Rocky Mountain Conference on Article 1 Analytical Chemistry July 1995 37th Rocky Mountain Conference on Analytical Chemistry Follow this and additional works at: https://digitalcommons.du.edu/rockychem Part of the Chemistry Commons, Materials Science and Engineering Commons, and the Physics Commons Recommended Citation (1995) "37th Rocky Mountain Conference on Analytical Chemistry," Rocky Mountain Conference on Magnetic Resonance: Vol. 37 , Article 1. Available at: https://digitalcommons.du.edu/rockychem/vol37/iss1/1 This work is licensed under a Creative Commons Attribution 4.0 License. This Article is brought to you for free and open access by Digital Commons @ DU. It has been accepted for inclusion in Rocky Mountain Conference on Magnetic Resonance by an authorized editor of Digital Commons @ DU. For more information, please contact [email protected],dig- [email protected]. et al.: 37th RMCAC Final Program and Abstracts 37TH ROCKY MOUNTAIN CONFERENCE ON ANALYTICAL CHEMISTRY FINAL PROGRAM AND ABSTRACTS JULY 23-27, 1995 HYATT REGENCY DENVER 1750 WELTON STREET DENVER, COLORADO SPONSORED BY: ROCKY MOUNTAIN SECTION SOCIETY FOR APPLIED SPECTROSCOPY & COLORADO SECTION AMERICAN CHEMICAL SOCIETY Published by Digital Commons @ DU, 1995 1 Rocky Mountain Conference on Magnetic Resonance, Vol. 37 [1995], Art. 1 TABLE OF CONTENTS Conference Organizers 2 Symposia Organizers 3 Registration and Event Information 5 Exhibitor List 8 Hotel and Visitor Information 9 Employment Clearing House and Professional Memberships 9 Short Courses 10 Vendor Workshops 12 Symposia Schedule: Atomic Spectroscopy 17 Chromatography 18 Compost (Biogeochemistry of) 19 Electrochemistry 20 Environmental Chemistry 22 EPR 25 FTIR/NIR/RAMAN Spectroscopy 37 General Posters 37 ICP-MS 39 Laboratory Safety 41 Luminescence 42 Mass Spectrometry 44 NMR 47 Pharmaceutical Analysis 59 Quality Assurance 60 Downtown Denver Street Map Inside back cover Abstracts start after page 61.
    [Show full text]
  • Synthesis and Reactions of 4,5-Homotropone and 4,5-Dimethylenetropone Richard Anthony Fugiel Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1974 Synthesis and reactions of 4,5-homotropone and 4,5-dimethylenetropone Richard Anthony Fugiel Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Fugiel, Richard Anthony, "Synthesis and reactions of 4,5-homotropone and 4,5-dimethylenetropone " (1974). Retrospective Theses and Dissertations. 5986. https://lib.dr.iastate.edu/rtd/5986 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]. INFORIVIATIOIM TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image.
    [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]
  • 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]
  • The Synthesis of Carbacyclic Silanes Via Organosilicon Reactive Intermediates Michael J
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1984 The synthesis of carbacyclic silanes via organosilicon reactive intermediates Michael J. Vuper Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Vuper, Michael J., "The synthesis of carbacyclic silanes via organosilicon reactive intermediates " (1984). Retrospective Theses and Dissertations. 7737. https://lib.dr.iastate.edu/rtd/7737 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]. INFORMATION TO USERS Tliis reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed.
    [Show full text]
  • William Von Eggers Doering's Remarkable Career - Personal Observations from the 1950S and '60S
    William von Eggers Doering's Remarkable Career - Personal Observations from the 1950s and '60s "... the questions themselves" Rainer Maria Rilke RONALD M. MAGID AND MAITLAND JONES, JR. Department of Chemistry, The University of Tennessee; Department of Chemistry, New York University Received Dedicated to Professor Bill Doering on the occasion of his 90th birthday ______________________________________________________________ ABSTRACT This Account consists of reminiscences about the Doering research group at Yale University, nearly a half-century ago. We recount vignettes and events that reflect the state of research in physical organic chemistry at that early time, the passion that drove Doering, and the lessons that he taught to his coworkers. We allude to specific research results that are described in considerable detail in the preceding article. _________________________________________________________________ In the accompanying article1 we describe some of the truly remarkable research accomplishments by Bill Doering and his coworkers over a 60-year-span. An editor, who may yet regret it, thought that it would be interesting to include some reminiscences by two of Bill's former graduate students. It was suggested that they might focus on the human side of the equation: what made Doering tick, how did the research group function, what was the nature of physical organic chemistry research and equipment in the 1950s-60s, etc. RMM and MJJr are the co-authors of this Account. Both were Yale undergraduates in Bill's introductory organic course in Spring-Fall, 1957, and both did their graduate work under Bill's supervision. MJJr's knowledge of Doering both precedes and supercedes the 1957-1963 period. Even before college, he had spent some summers at Hickrill Chemical Research Laboratory (about which much more, soon).
    [Show full text]