Dossier Sur Les Travaux Scientifiques De Guy Bertrand
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UC San Diego Electronic Theses and Dissertations
UC San Diego UC San Diego Electronic Theses and Dissertations Title Development and Reactivity Studies of Highly Ambiphilic Carbenes Permalink https://escholarship.org/uc/item/57t561ss Author Weinstein, Cory Publication Date 2018 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California UNIVERSITY OF CALIFORNIA, SAN DIEGO Development and Reactivity Studies of Highly Ambiphilic Carbenes A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry by Cory Michael Weinstein Committee in charge: Guy Bertrand, Chair Michael K. Gilson Joseph M. O’Connor Arnold L. Rheingold Haim Weizman 2018 Copyright Cory Michael Weinstein, 2018 All rights reserved The dissertation of Cory Michael Weinstein is approved, and it is acceptable in quality and form for publication on microfilm and electronically: Chair University of California, San Diego 2018 iii DEDICATION This dissertation is dedicated to my mom Without her endless sacrifices and unconditional love and support Nothing I have ever done would have been possible iv EPIGRAPH “luck is always better than skill at things” -James Murphy but “chance favors the prepared mind” -Louis Pasteur v TABLE OF CONTENTS Signature Page ............................................................................................................................................. iii Dedication ................................................................................................................................................... -
A Dicationic Iminophosphane Ying Kai Loh, Chitra Gurnani, Rakesh Ganguly, and Dragoslav Vidović*
A Dicationic Iminophosphane Ying Kai Loh, Chitra Gurnani, Rakesh Ganguly, and Dragoslav Vidović* Department of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371. Supporting Information Placeholder ABSTRACT: A novel dicationic system containing a PN frag- ment has been synthesized and structurally characterized. Accord- ing to the solid state analysis and theoretical investigation the dica- tionic iminophosphane resonance from is the most appropriate de- scription for the dication. However, the contribution from the phos- phorus mononitride resonance form is not negligible. Neutral two-eletron donor carbenes have proven to be quite versatile ligands for isolation of a wide variety of novel main group 1-4 species. Examples include diatomic allotropes (L-E2-L; L = car- bene, E = B, Si, Ge, P, As, etc)1a of boron, silicon, germanium, phosphorus, arsenic, etc.2-4 Nevertheless, these interesting mole- cules, among numerous other main group species, sparked a debate about the most appropriate way to describe bonding in these com- Figure 1. Recently isolated neutral (A) and radical cationic (B) 5,6 pounds. In particular, the arguments have been focused on phosphorus mononitrides, and general structure for carbones (C). whether the carbene moieties form typical covalent bonds or the Dipp = 2,6-diisopropylphenyl. use of dative bond analogy is also valid. The latest evidence showed that the L-E bonds for L-B2-L are quite strong suggesting a sub- stantial covalent character.6 However, Frenking argued that dative The overall synthesis of the target dication is summarized in bonds could be also very strong by the combination of -donation Scheme 1. -
Injection of Meteoric Phosphorus Into Planetary Atmospheres
Planetary and Space Science 187 (2020) 104926 Contents lists available at ScienceDirect Planetary and Space Science journal homepage: www.elsevier.com/locate/pss Injection of meteoric phosphorus into planetary atmospheres Juan Diego Carrillo-Sanchez a, David L. Bones a, Kevin M. Douglas a, George J. Flynn b, Sue Wirick c, Bruce Fegley Jr. d, Tohru Araki e, Burkhard Kaulich e, John M.C. Plane a,* a School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK b State University of New York at Plattsburgh, Department of Physics, 101 Broad Street, Plattsburg, NY, 12901, USA c Focused Beam Enterprises, Westhampton, NY, 11977, USA d Planetary Chemistry Laboratory, Department of Earth & Planetary Sciences and McDonnell Center for the Space Sciences, Washington University, St Louis, MO, 63130, USA e Diamond Light Source Ltd, Harwell Science & Innovation Campus, Didcot, OX11 0DE, UK ARTICLE INFO ABSTRACT Keywords: This study explores the delivery of phosphorus to the upper atmospheres of Earth, Mars, and Venus via the Cosmic dust ablation of cosmic dust particles. Micron-size meteoritic particles were flash heated to temperatures as high as Planetary atmospheres 2900 K in a Meteor Ablation Simulator (MASI), and the ablation of PO and Ca recorded simultaneously by laser Ablation induced fluorescence. Apatite grains were also ablated as a reference. The speciation of P in anhydrous chondritic Phosphorus thermodynamics porous Interplanetary Dust Particles was made by K-edge X-ray absorption near edge structure (XANES) spec- Zodiacal cloud troscopy, demonstrating that P mainly occurs in phosphate-like domains. A thermodynamic model of P in a sil- icate melt was then developed for inclusion in the Leeds Chemical Ablation Model (CABMOD). -
13C NMR-Study of 1,1-Dipotassio-2,3,4,5
J. Chosun Natural Sci. Vol. 10, No. 3 (2017) pp. 131 − 136 https://doi.org/10.13160/ricns.2017.10.3.131 13C NMR-Study of 1,1-Dipotassio-2,3,4,5-Tetraphenyl-1-Silacyclopentadienide 2− + Dianion [SiC4Ph4] •2[K ] and 1,1-Dipotassio-2,3,4,5-Tetraphenyl-1- 2− + Germacyclopentadienide Dianion [GeC4Ph4] •2[K ] Jang-Hwan Hong† Abstract 13 2− + The chemical shifts in the C NMR spectra of 2,3,4,5-tetraphenyl-1-silacyclopentdienide dianion [SiC4Ph4] •2[K ] (3) 2− + 2− + and 2,3,4,5-tetraphenyl-1-germacyclopentdienide dianion [GeC4Ph4] •2[K ] (4) were compared to those of [SiC4Ph4] •2[Li ] 2− + 2− + (5), [SiC4Ph4] •2[Na ] (6), and [GeC4Ph4] •2[Li ] (7). The average polarizations in two phenyl groups of two potassium 2− + salts are decreased over 15% to 20% comparing to those of the lithium salts and sodium salt {[EC4Ph4] •2[M ] (E=Si, Ge, M=Li, Na) due to the effect of the counter potassium cation. Keywords: Silole, Germole, Dianion, Aromaticity, Potassium 1. Introduction aromatic[5, 6] (Scheme 1). In these points it is very interesting to find out any The last decades have witnessed tremendous progresses effect of counter-cation to the aromaticity of 2,3,4,5- in the field of group 14 metallole dianions and the related tetraphenyl substituted silole dianion or germole dianion. metallole anions[1-6] since the first silole dianion had been Meanwhile there is no report for the effect of the reported[7]. In particular the syntheses and characteriza- counter-cation in group 14 metallole dianions as long as 1− tions of the silole anion [1-tert-butyl-SiC4Ph4] , the silole we know honestly until now. -
Novel Alkyne and Phosphaalkyne Coupling on an Ir4 Cluster: Synthesis and Molecular Structure of [Ir4(P-CO)(CO)7{P4-T13-Ph,PC(H)C(Ph)Pcbut}(P-Pph2)1 Maria Helena A
View Article Online / Journal Homepage / Table of Contents for this issue J. CHEM. SOC., CHEM. COMMUN., 1994 1869 Novel Alkyne and Phosphaalkyne Coupling on an Ir4 Cluster: Synthesis and Molecular Structure of [Ir4(p-CO)(CO)7{p4-t13-Ph,PC(H)C(Ph)PCBut}(p-PPh2)1 Maria Helena A. Benvenutti,asb Peter B. Hitchcock,b John F. Nixon*b and Maria D. Vargas*d a lnstituto de Quimica, Universidade Estadual de Campinas, CP 6154, Campinas, 13083, SP, Brazil b School of Chemistry and Moiecular Sciences, University of Sussex, Brighton, UK BN 1 9QJ The cluster compound [(p-H)Ir4(CO),(Ph2PCCPh)(p-PPh2)]1 reacts with the phosphaalkyne ButCP to yield [Ir4(p-CO)(CO),{p~-113-Ph2PC(H)C(Ph)PCBut}(p-PPh2)]3, containing the novel 2-phosphabutadienylphosphine fragment as a result of the coupling of ButCP with the diphenylphosphinoalkyne ligand and incorporation of the cluster bound H atom. There are relatively few examples of controlled alkyne-alkyne between the Ph2PCCPh ligand and the ButCP molecule, and coupling reactions at polynuclear carbonyl clusters.' The hydride migration to the resulting new phosphorus carbon chemistry of phosphaalkynes, RCP, is of considerable con- chain were established by 'H, 31P and 13C NMR spectroscopy. temporary interest and their similarity to alkynes has been In spite of the detailed spectroscopic studies undertaken, it stressed previously.2 There is only one reported interaction was impossible to establish unambiguously the position of the between an alkyne and a phosphaalkyne, leading to a hydrogen atom in the chain, and whether the diphenylphos- mononuclear 774-1-phosphacyclobutadienecomplex described phinoalkyne had undergone P-C,, bond cleavage. -
Conjugated Materials Containing Dithienometalloles
Conjugated materials containing dithienometalloles Joshua Paul Green Submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Physics Imperial College London September 2016 Declaration The work presented herein was carried out at the Chemistry Department of Imperial College London between October 2012 and September 2016 under the supervision of Professor Martin Heeney. Except where otherwise stated, all work was performed by me. Joshua P. Green, September 2016 ii Contributions This work would not have been possible without the people below, to whom I send my whole-hearted thanks. The organic field effect transistors discussed in Chapters 2 and 4 were prepared and tested by Dr. Yang Han at Imperial College London. Organic photovoltaic devices (Chapter 3) were tested by Dr. Hyojung Cha and Dr. Pabitra Tuladhar at Imperial College London. The X-ray diffraction measurements in Chapter 2 were carried out by Rebecca Kilmurray at Imperial College London. Photoelectron spectroscopy in air measurements were carried out by Adam Creamer at CSIRO (Melbourne, Australia). Finally, I would like to thank Sam Cryer, Dr. Abby Casey, and Dr. Zhuping Fei for providing starting materials and polymers used in Chapters 2, 3, and 4, respectively. Additional thanks must go to Haojie Dai for his help with the work discussed in Chapter 5 during his time as my student in his Master’s year. iii Copyright Declaration The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non-Commercial No Derivatives licence. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. -
Intermediate Oxidation State Tungsten Acetylacetonate Complexes
Intermediate Oxidation State Tungsten Acetylacetonate Complexes Chetna Khosla A dissertation submitted to the faculty of the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry. Chapel Hill 2009 Approved by: Advisor: Professor Joseph L. Templeton Reader: Professor Maurice Brookhart Reader: Professor Cynthia Schauer Professor Valerie Ashby Professor H. Holden Thorp ABSTRACT Chetna Khosla: INTERMEDIATE OXIDATION STATE TUNGSTEN ACETYLACETONATE COMPLEXES (Under the direction of Professor Joseph L. Templeton) Previous work with tungsten(II) acetylacetonate complexes has focused on synthesis of complexes with -bound ligands (alkyne, nitrile, imine, ketone, aldehyde). In this work, 2 addition of methyl triflate (MeOTf) to W(CO)(acac)2(η -N≡CPh) produces the iminoacyl 2 complex [W(CO)acac)2(η -MeN=CPh)][OTf]. Displacement of the carbon monoxide in 2 + [W(CO)(acac)2(η -MeN≡CPh)] by isonitriles, bulky phosphines, and alkynes has been accomplished. The substitution of carbon monoxide by alkyne relieves the iminoacyl ligand of its role as a four-electron donor and enables further reduction of the C-N based ligand. Use 2 + of Na[HB(OMe)3] as a hydride source that attacks [W(RC≡CR′)(acac)2(η -MeN=CPh)] 2 yields the imine complex W(RC≡CR′)(acac)2(η -MeN=CHPh) with a diastereoselective ratio of 2:1. Addition of MeOTf leads to the final tungsten(II) iminium complex 2 [W(RC≡CR′)(acac)2(η -Me2N=CHPh)][OTf]. 2 Addition of m-chloroperoxybenzoic acid (MCPBA) to W(CO)(acac)2(η -N≡CR) 2 2 results in oxidation of the metal center to form the W(IV) d metal complex W(O)(acac)2(η - N≡CR). -
Developing the Catalytic Asymmetric Hydroarsination Reaction
This document is downloaded from DR‑NTU (https://dr.ntu.edu.sg) Nanyang Technological University, Singapore. Developing the catalytic asymmetric hydroarsination reaction Tay, Wee Shan 2020 Tay, W. S (2020). Developing the catalytic asymmetric hydroarsination reaction. Doctoral thesis, Nanyang Technological University, Singapore. https://hdl.handle.net/10356/142898 https://doi.org/10.32657/10356/142898 This work is licensed under a Creative Commons Attribution‑NonCommercial 4.0 International License (CC BY‑NC 4.0). Downloaded on 11 Oct 2021 05:24:27 SGT DEVELOPING THE CATALYTIC ASYMMETRIC HYDROARSINATION REACTION TAY WEE SHAN SCHOOL OF PHYSICAL AND MATHEMATICAL SCIENCES 2020 DEVELOPING THE CATALYTIC ASYMMETRIC HYDROARSINATION REACTION TAY WEE SHAN SCHOOL OF PHYSICAL AND MATHEMATICAL SCIENCES A thesis submitted to the Nanyang Technological University in partial fulfilment of the requirement for the degree of Doctor of Philosophy 2020 Statement of Originality I hereby certify that the work embodied in this thesis is the result of original research done by me except where otherwise stated in this thesis. The thesis work has not been submitted for a degree or professional qualification to any other university or institution. I declare that this thesis is written by myself and is free of plagiarism and of sufficient grammatical clarity to be examined. I confirm that the investigations were conducted in accord with the ethics policies and integrity standards of Nanyang Technological University and that the research data are presented honestly and without prejudice. 7 July 2020 . Date Tay Wee Shan Supervisor Declaration Statement I have reviewed the content and presentation style of this thesis and declare it of sufficient grammatical clarity to be examined. -
Synthesis and Characterization of Luminescent Cyclic Germanium Compounds Teresa Lynn Bandrowsky University of Missouri-St
University of Missouri, St. Louis IRL @ UMSL Dissertations UMSL Graduate Works 5-17-2013 Synthesis and Characterization of Luminescent Cyclic Germanium Compounds Teresa Lynn Bandrowsky University of Missouri-St. Louis Follow this and additional works at: https://irl.umsl.edu/dissertation Part of the Chemistry Commons Recommended Citation Bandrowsky, Teresa Lynn, "Synthesis and Characterization of Luminescent Cyclic Germanium Compounds" (2013). Dissertations. 309. https://irl.umsl.edu/dissertation/309 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 Synthesis and Characterization of Luminescent Cyclic Germanium Compounds by Teresa Bandrowsky A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Chemistry) University of Missouri – St. Louis May 2013 Abstract Synthesis and Characterization of Luminescent Cyclic Germanium Compounds The vision in the field of organic electronics is the realization of flexible, easily manufactured, low cost optoelectronics for use in organic light emitting diodes (OLEDs) for large area displays and lighting applications, organic photovoltaic cells, and organic field-effect transistors. The active layers within such devices are composed of semiconducting small molecules or polymers. The rich chemistry of new π-conjugated materials holds the key to continued progress by allowing the material properties of organic semiconductors to be readily tuned towards application specific demands. In order for these materials to be useful in device applications, they must exhibit high stability, electron mobility and quantum efficiency. -
Article Mesoionic Carbene-Breslow Intermediates As Super Electron Donors: Application to the Metal-Free Arylacylation of Alkenes
ll Article Mesoionic carbene-Breslow intermediates as super electron donors: Application to the metal-free arylacylation of alkenes Wei Liu, Adam Vianna, Zengyu Zhang, ..., Mohand Melaimi, Guy Bertrand, Xiaoyu Yan [email protected] (G.B.) [email protected] (X.Y.) Highlights Breslow intermediates derived from mesoionic carbenes are super electron donors A mesoionic-carbene-catalyzed arylacylation of alkenes is described Facile construction of complex carbonyl compounds from simple substrates Breslow intermediates derived from mesoionic carbenes (BIMICs) are highly reductive species able to reduce iodoarenes under ambient condition. The reductive power of BIMICs allows for the use of mesoionic carbenes as powerful catalysts in the inter- and intramolecular arylacylation of alkenes. Liu et al., Chem Catalysis 1,1–11 June 17, 2021 ª 2021 Elsevier Inc. https://doi.org/10.1016/j.checat.2021.03.004 Please cite this article in press as: Liu et al., Mesoionic carbene-Breslow intermediates as super electron donors: Application to the metal-free arylacylation of alkenes, Chem Catalysis (2021), https://doi.org/10.1016/j.checat.2021.03.004 ll Article Mesoionic carbene-Breslow intermediates as super electron donors: Application to the metal-free arylacylation of alkenes Wei Liu,1 Adam Vianna,2 Zengyu Zhang,1 Shiqing Huang,1 Linwei Huang,1 Mohand Melaimi,2 Guy Bertrand,2,3,* and Xiaoyu Yan1,* SUMMARY The bigger picture Classical N-heterocyclic carbenes (NHCs), such as thiazolylidenes, N-Heterocyclic carbenes (NHCs) 1,2,4-triazolylidenes, and imidazol(in)-2-ylidenes, are powerful or- have been demonstrated to be ganocatalysts for aldehyde transformations through the so-called powerful organocatalysts for Breslow intermediates (BIs). -
Lowcoordinated Silicon and Hypercoordinated Carbon
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 557 Lowcoordinated Silicon and Hypercoordinated Carbon Structure and Stability of Silicon Analogs of Alkenes and Carbon Analogs of Silicates ANDERS M. EKLÖF ACTA UNIVERSITATIS UPSALIENSIS ISSN 1651-6214 UPPSALA ISBN 978-91-554-7294-8 2008 urn:nbn:se:uu:diva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
Catalytic Main Group Element Bond Formation Reactions Toward the Preparation of Conjugated Materials Neil Mucha University of Vermont
University of Vermont ScholarWorks @ UVM Graduate College Dissertations and Theses Dissertations and Theses 2015 Catalytic Main Group Element Bond Formation Reactions Toward the Preparation of Conjugated Materials Neil Mucha University of Vermont Follow this and additional works at: https://scholarworks.uvm.edu/graddis Part of the Inorganic Chemistry Commons Recommended Citation Mucha, Neil, "Catalytic Main Group Element Bond Formation Reactions Toward the Preparation of Conjugated Materials" (2015). Graduate College Dissertations and Theses. 469. https://scholarworks.uvm.edu/graddis/469 This Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks @ UVM. It has been accepted for inclusion in Graduate College Dissertations and Theses by an authorized administrator of ScholarWorks @ UVM. For more information, please contact [email protected]. CATALYTIC MAIN GROUP ELEMENT BOND FORMATION REACTIONS TOWARD THE PREPARATION OF CONJUGATED MATERIALS A Dissertation Presented by Neil Thomas Mucha to The Faculty of the Graduate College of The University of Vermont In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Specializing in Chemistry October, 2015 Defense Date: July 23, 2015 Dissertation Examination Committee: Rory Waterman, Ph. D., Advisor Qingbin Wang, Ph. D., Chairperson Christopher C. Landry, Ph. D. Adam C. Whalley, Ph. D. Cynthia J. Forehand, Ph. D., Dean of the Graduate College ABSTRACT Polymers incorporating main group elements offer different and interesting properties compared to their all carbon analogues. For example, π-conjugated polymers incorporating phosphorus in the main chain of the polymer have generated interest due to their unique thermal and electronic properties, which primarily result from delocalization of the phosphorous lone pair within aromatic units.