DOCSLIB.ORG

HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES for SELECTIVE CATALYSIS Alberto Martínez Lombardía

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES for SELECTIVE CATALYSIS Alberto Martínez Lombardía HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral. No se autoriza su reproducción u otras formas de explotación efectuadas con fines lucrativos ni su comunicación pública desde un sitio ajeno al servicio TDR. Tampoco se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al contenido de la tesis como a sus resúmenes e índices. WARNING. Access to the contents of this doctoral thesis and its use must respect the rights of the author. It can be used for reference or private study, as well as research and learning activities or materials in the terms established by the 32nd article of the Spanish Consolidated Copyright Act (RDL 1/1996). Express and previous authorization of the author is required for any other uses. In any case, when using its content, full name of the author and title of the thesis must be clearly indicated. Reproduction or other forms of for profit use or public communication from outside TDX service is not allowed. Presentation of its content in a window or frame external to TDX (framing) is not authorized either. These rights affect both the content of the thesis and its abstracts and indexes. UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía ALBERTO MARTÍNEZ LOMBARDÍA HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS DOCTORAL THESIS Supervised by Prof. Dr. Carmen Claver and Dr. Cyril Godard Departament de Química Física I Inorgànica Tarragona, June 2016 UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía Departament de Química Física i Inorgànica, Facultat de Química C/ Marcel·lí Domingo s/n, 43007, Tarragona Prof. Dr. Carmen Claver Cabrero, and Dr. Cyril Godard from the Department of Physical and Inorganic Chemistry at Universitat Rovira I Virgili, STATE that the present study, entitled “Heterogenized N-Heterocyclic Carbenes Transition Metal Complexes for Selective Catalysis”, presented by Alberto Martínez Lombardía for the award of the degree of Doctor, has been carried out under our supervision at the Department of Physical and Inorganic Chemistry at Universitat Rovira I Virgili and that it fulfils all the requirements to be eligible for the International Doctorate Award. Tarragona, 10 May, 2016 Doctoral Thesis Supervisor/s Prof. Dr. Carmen Claver Cabrero Dr. Cyril Godard UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía The present Doctoral Thesis has been carried out thanks to the “Programa d’ajuts per a la contractació de personal investigador novell (FI-DGR) (Reference: 2011F1_B2 00216) financed by the Generalitat de Catalunya. The work developed in this doctoral thesis has been possible thanks to the finantial support from the following research projects: - 246461 SYNFLOW European 7th Framework Programme - CTQ2010-14938 - 2009 SGR 116 - CTQ2013-43438-R - 2014 SGR 670 UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía ACKNOWLEDGEMENTS En primer lugar, quiero agradecerles a Carmen y a Cyril la oportunidad que me han brindado de poder llevar a cabo una tesis doctoral en su grupo. A Cyril, te agradezco lo mucho que he aprendido durante estos años, tu accesibilidad y tu ayuda la hora de resolver problemas de química. A Carmen, te agradezco mucho tu apoyo, tu confianza, tu cercanía a pesar de tu apretada agenda y el exquisito trato recibido. Y por supuesto, las incontables oportunidades que se me han puesto al alcance durante estos años, congresos, conferencias, estancias… Gracias por fomentar siempre el buen ambiente y motivarnos con cenas de navidad llenas de villancicos, cenas de verano en el jardín, excursiones al valle… Gracias a Eduardo Peris por darme la oportunidad de conocer el mundo de la investigación, y por posibilitar mi estancia Erasmus en Toulouse, y por ayudarme a recalar en Tarragona para así poder hacer la tesis. Aunque dudo que lo lea nunca, muchas gracias a Jamin, por empezar la química a la que he dedicado buena parte de estos 4 años, y por enseñarme a trabajar en el laboratorio con un rigor que yo no tenía. Le quiero agradecer a Sergio Castillón su disponibilidad, su trato auténtico, y sus fantásticas explicaciones, provistas de fundamento y utilidad práctica, cosas ambas no siempre compatibles en un laboratorio. Quiero agradecer a todos los compañeros que he tenido durante estos 4 años y medio, ya que todos me han aportado algo de una forma u otra. Gente del mundo boro, Amadeu y su pedazo cena de tesis en el restaurante Gaudir, Henrik y sus horarios tarde-noche y su amabilidad, Cristina Pubill poniendo reacciones con su camisa de cuadros y riéndose por todo, Jess Cid y su sentido del humor siempre a punto, Cristy Solé, la energía incontenible, Xavi Sanz “com li fots” XD, Yérard y su asombrosa habilidad con los idiomas y las imitaciones, Enrico, sangre siciliana, Ana B, 10 como química, 11 como persona…, los baby borons Nuria y sus anillos, Marc petit y sus complicados compuestos, y Jordi Royes el del Madriz XD, Alba que estuvo poquito tiempo, Adam, que UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía vino de estancia, y Eric Bowes, cómo te lo montas, gran reencuentro en Ottawa :D Azucarillos (oscarcitos), Javi Mazuela, pásate algún paper, Mercé y su amor por los animales, Sabina, Magre, alcalde de Valls, Jèeessica M, lo milloret del Perelló, Charly, todo clase y espectaculares raquetukis en Sapeira, Maria, la mejor calçotada de mi vida, Zahra, la alegría en persona, Albert, un crak del nàstic, Efrem y Carles, todo por delante. Gente CO2, Siham, Marlene, encantadora como siempre 4 años después, Laia, danza del vientre de Els Pallaresos, Anna M Masdeu, siempre buen rollo. Carmencitos, Angy y Vero, Bernabé, “no tocar” “Bernabé”, Jessi, Eli, mítica, gatitos, cristales por doquier, criadora de pollos como yo por ejemplo, Franciscooooooo el hípster madrugador de Reus capital, Nanette, se te echa en falta, Antón, ya te quedan menos columnas XD ;) J Creus, gracias por traerme ligandos en vialitos desde Barcelona, Laura y Aarón, se os quiere, Myriam, welcome to the jungleeeee nananananana, Carmencitos de la acera de enfrente (CTQ), Quique, Doctor Colavida, VAMOS!!!!! Jorge, soluciona problemas, y baila, Bianca y Mónica, Repsol se os queda muy pequeño, Dolores, Stefano, no le puedes caer mal a nadie, Xavi Castilla, se echan en falta las quedadas toulousans, a ver si nos vemos pronto, Olga, Míriam de los apellidos muy largos, Isabel y Aitor, parejita feliz, Olivia, Itzi, gracias por buscarme amigos en Bilbo por Navidad y por tener tanto flow ;) Vamos con el staff, Raquel por ser una crack y la number one de los técnicos de la uni, Josep, siempre un placer poder contar contigo. Sílvia, siempre me has echado una manita con lo que sea, Yolanda, también, gracias por preocuparte por mi beca, Elisenda, gracias por todo, siempre me has solucionado la papeleta. Ramón, paciencia, bondad y eficiencia a partes iguales. Toni de la Torre, gracias por buscarme un hueco siempre para hacer ICPs… Débora, gracias por ser tan atenta y tan simpática. I’d like to say thank you to Giancarlo Franciò for being my advisor and helping me during my time in Aachen, and also to Walter Leitner for the great opportunity to spend three months at the ITMC. En el terreno UNIVERSITAT ROVIRA I VIRGILI HETEROGENIZED N-HETEROCYCLIC CARBENE METAL COMPLEXES FOR SELECTIVE CATALYSIS Alberto Martínez Lombardía personal conocí a gente de la que no me voy a olvidar. Maren, I felt like home during my time in Aachen (actually better than at home). Really one the best periods in my life, just thanks for everything, hope to keep in contact and get the chance to share some more fabulous times :D .
Load more

Recommended publications
  • Toward Thermodynamically Stable Triplet Carbenes Yumiao Ma* BSJ Institute, Haidian, Beijing, 100084 [email protected] Abstr
    Toward Thermodynamically Stable Triplet Carbenes Yumiao Ma* BSJ Institute, Haidian, Beijing, 100084 [email protected] Abstract In sharp contrast to the widely studied and applied stable singlet carbenes, only several kinetically persistent triplet carbenes have been studied, and thermodynamically stable triplet carbenes are much less developed. With the Gibbs free energy of C-H bond insertion into methane as a probe, DFT calculations were employed to examine a variety of candidate molecules for stable triplet carbenes. Guided by these calculations, some molecules with significant stability against C-H insertion were designed by fine tuning of geometry and electronic structures. These compounds might be potential candidates for experimental development of stable triplet carbenes. Introduction Pioneered by Guy Bertrand, Armin Arduengo and others, stable singlet carbenes have been well developed since 1980s1-3, and have exhibited great importance as ligands, reagents, etc. On the other hand, stable, or even kinetically persistent triplet carbenes are still scarce. A persistent triplet carbene, 2, 2', 4, 4', 6, 6'-hexabromodiphenylcarbene, was reported by Hideo Tomioka et al in 19954, with a half-life at ~1 s. In 2001, persistent triplet carbene with half-life of 19 min at room temperature was reported5, which was a great breakthrough. Several other kinetically persistent triplet carbenes were also studied, and the half-life ranges from microseconds to a week6, 7. However, thermodynamically stable triplet carbenes are still unknown hitherto, to the best of our knowledge. In this work, a variety of potential candidates for stable triplet carbenes were designed and examined by quantum chemical calculations. Guided by calculations and rational design, some competitive candidates were obtained, which may be helpful for the development of stable triplet carbenes, and for the understanding of the chemical properties related to open shell organic compounds.
    [Show full text]
  • Copyrighted Material
    275 Index a antiaromatic systems acetals and hemiacetals – benzo-annulation 264 – aldehyde hydrates 267 – compounds 262–263 – chloral hydrate 267 – cyclobutadiene 263 – cyclohexanone hydrate 267 – cyclooctatetraene 264 – cyclopropanones 267, 268 – cyclopropene 263 – definitions 267 – 3-cyclopropenyl anion 263 – formation mechanisms 268, 269 – dimerization 263–264 – protecting group 268, 269 – energetically destabilized, conjugation activation energy 17 262, 264 addition reactions, carbenes aryne–metal complexes 227–228 – bicyclic olefins 172–173 arynes – carbene to alkene, stereospecific – 1,2-, 1,3-and 1,4-didehydrobenzenes addition 170 229–230 – dibromocarbene 168, 169 – allylic hydrogen 228 – hexafluorobenzene 172, 173 – 1-aminobenzotriazole, oxidation 235 – pyrroles and indoles 172, 173 – benzenediazonium-2-carboxylate 232, – Simmons–Smith reactions 174, 175 233–234 – Simmons–Smith reagent 173–174 – Bergman cyclization 229 – singlet carbenes 168, 169 – coupled cluster (CC) 225 – stereochemistry 170–171, 172 – cycloaddition reactions 227, 240–243 – stereoselectivity 173 – density functional theory (DFT) 225 – triplet carbenes 168, 169–170 – 1,3-dipolar cycloaddition 243–244 aldol condensation – generation 230 – aldehyde/ketone 78, 79 – and heteroarynes 225 – aromatic ketones 78, 79 – isolable zwitterion 234 – Claisen condensation 78, 80 – lowest unoccupied molecular orbitals – Dieckmann condensation 80 (LUMOs) 227 – esters 78 – meta-benzyne 228, 229 – fluoroacetonitrileCOPYRIGHTED 78, 79 – nomenclature MATERIAL 226 – Knoevenagel condensation 81 – nucleophilic addition 237–238 – Michael reaction 81 – in organic synthesis 245–246 alkene 30 – ortho-, meta-and para-benzynes alkyl and dialkyl carbenes 185 227 allenes (cycloaddition to 1,2-dienes) – ortho-benzyne 226 176 – para-benzyne 228, 229 allylic hydrogen 228 – reactions 228 amine 29–30 – representative 226 Reactive Intermediates in Organic Chemistry: Structure, Mechanism, and Reactions, First Edition.
    [Show full text]
  • Organocatalysis with N-Heterocyclic Carbenes
    Organocatalysis with N-Heterocyclic Carbenes Frontiers of Chemistry Robert B. Lettan II March 28th, 2009 Key References: Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107, 5606-5655. Marion, N.; Díez-González, S.; Nolan, S. P. Angew. Chem. Int. Ed. 2007, 46, 2988-3000. Johnson, J. S. Curr. Opinion Drug. Discov. Develop. 2007, 10, 691-703. Rob Lettan @ Wipf Group Page 1 of 34 3/30/2009 Thiamine-Dependent Enzymes NH 2 Me N OR Thiamine: R = H N 3— TPP: R = P2O6 S Me N H Thiamine diphosphate (TPP) is required by a number of enzymes that catalyze the cleavage and formation of bonds to the carbon atom of a carbonyl group. Mechanism of pyruvate decarboxylase (PDC) Me Me N Me N OR HO N N pyruvate Me S —CO2 Me NH2 S Me H O O N N HO S H S Me N Me Me carbene Me H N OR ylide N N O H S NH H Me S Me H All 3 nitrogens on aminopyridine ring OH involved in hydrogen binding to enzyme. Jordan, F. Nat. Prod. Rep. 2003, 20, 184-201. Rob Lettan @ Wipf Group Page 2 of 34 3/30/2009 Thiamine-Dependent Enzymes Rob Lettan @ Wipf Group Page 3 of 34 3/30/2009 Thiamine-Dependent Enzymes Mechanism of pyruvate dehydrogenase (E1) Me Me N Me pyruvate N N N HO —CO2 S NH2 S E1 Me carbene ylide S S H N E2 O SH H O FADH2 NAD N lipoamide Me S E2 O E3 SH H FAD NADH CoASH N E2 HS E2 O O Krebs cycle How can nature’s Umpolung method cellular Me SCoA of bond-formation be applied to synthesis? respiration Acetyl-CoA Leeper, F.
    [Show full text]
  • Communicatio N In
    COMMUNICATIOUS009932315B2 N IN ( 12 ) United States Patent ( 10 ) Patent No. : US 9 , 932 ,315 B2 Johnson et al. (45 ) Date of Patent: Apr . 3 , 2018 ( 54 ) PERSISTENT CARBENE ADDUCTS AND FOREIGN PATENT DOCUMENTS RELATED METHODS WO WO 00 /071554 A2 11/ 2000 wo WO 02 /076613 Al 10 / 2002 ( 71 ) Applicant : Massachusetts Institute of Wo WO 2008 / 069688 A2 6 / 2008 Technology , Cambridge , MA (US ) WO WO 2012 / 002913 AL 1 /2012 (72 ) Inventors : Jeremiah A . Johnson , Boston , MA OTHER PUBLICATIONS (US ) ; Aleksandr V . Zhukhovitskiy , El Cerrito , CA (US ) International Search Report and Written Opinion for PCT/ US15 / 44295 dated Nov . 13 , 2015 . International Preliminary Report on Patentability for PCT/ US15 / ( 73 ) Assignee : Massachusetts Institute of 44295 dtaed Feb . 23 , 2017 . Technology, Cambridge , MA (US ) Kuchenbeiser , Reactivity of Bis ( amino )cyclopropenylidenes ( BACs ) and Cyclic ( alkyl ) (amino )carbenes ( CAACs) . UC Riverside @( * ) Notice : Subject to any disclaimer , the term of this Electronic Theses and Dissertations. Aug. 2009 217 pages . Last accessed on Apr. 20 , 2017 at < http : // escholarship . org/ uc / item / patent is extended or adjusted under 35 6h67q1f4 > . U . S . C . 154 ( b ) by 0 days . Dyker et al. , Soluble Allotropes of Main - Group Elements . Science . Aug . 22 , 2008 ;321 (5892 ) : 1050 - 1 . ( 21 ) Appl. No. : 15 /502 , 678 Kuhn et al ., A Facile Preparation of Imidazolinium Chlorides . Org . Lett . 2008 ; 10 ( 10 ) : 2075 - 7 . Epub Apr. 16 , 2008 . ( 22 ) PCT Filed : Aug. 7 , 2015 Kuhn et al. , 1, 3 - Diisopropyl - 4 , 5 - dimethylimidazolium - 2 - N , N ’ diisopropylamidinat , ein neuartiges Betain . Zeitschrift für Naturforschung B . Apr . 1999 ; 54 ( 4 ) :434 - 40 .
    [Show full text]
  • Synthesis of Transition Metal N-Heterocyclic Carbene Complexes and Applications in Catalysis
    Université de Montréal Synthesis of Transition Metal N-Heterocyclic Carbene Complexes and Applications in Catalysis Par Michael Holtz-Mulholland Département de chimie Faculté des arts et des sciences Thèse présentée à la Faculté des études supérieures et postdoctorales en vue de l’obtention du grade de philosophiæ doctor (Ph.D.) en chimie Août, 2014 © Michael Holtz-Mulholland, 2014 Université de Montréal Faculté des études supérieures et postdoctorales Cette thèse intitulée: Synthesis of Transition Metal N-Heterocyclic Carbene Complexes and Applications in Catalysis Présentée par: Michael Holtz-Mulholland A été évaluée par un jury composé des personnes suivantes: Pr. Davit Zargarian, président-rapporteur Pr. Shawn K. Collins, directeur de recherche Pr. André B. Charette, membre du jury Pr. Bruce A. Arndtsen, examinateur externe Pr. David Morse, représentant du doyen de la FAS Abstract A new class of C1-symmetric N-heterocyclic carbene (NHC) ligands has been developed. The new ligands exploit a biaryl methyne as a chiral relay, and an N-methyl group as a reactivity controlling element. The precursors for the new ligands were synthesized via a modular scheme that allows for facile diversification. Several of the new ligands were installed onto both copper and gold, generating mono N-heterocyclic carbene transition metal complexes. The new C1-symmetric copper complexes were tested as catalysts for the synthesis of binaphthols via the oxidative coupling of electron poor 2-naphthols. The new C1-symmetric ligands afforded higher yields than their C2-symmetric counterparts. During the course of the optimization, small molecule additives were found to modulate the reactivity of the copper catalyst.
    [Show full text]
  • Downloaded on 2017-02-12T05:57:30Z Theoretical Chemistry Accounts Manuscript No
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Cork Open Research Archive Title Copper(I) carbene hydride complexes acting both as reducing agent and precursor for Cu ALD: a study through density functional theory Author(s) Dey, Gangotri; Elliott, Simon D. Publication date 2013-11-14 Original citation DEY, G. & ELLIOTT, S. D. 2013. Copper(I) carbene hydride complexes acting both as reducing agent and precursor for Cu ALD: a study through density functional theory. Theoretical Chemistry Accounts, 133, 1-7. http://dx.doi.org/10.1007/s00214-013-1416-y Type of publication Article (peer-reviewed) Link to publisher's http://dx.doi.org/10.1007/s00214-013-1416-y version Access to the full text of the published version may require a subscription. Rights © Springer-Verlag Berlin Heidelberg 2013. The final publication is available at Springer http://dx.doi.org/10.1007/s00214-013-1416-y Item downloaded http://hdl.handle.net/10468/2476 from Downloaded on 2017-02-12T05:57:30Z Theoretical Chemistry Accounts manuscript No. (will be inserted by the editor) Copper(I) carbene hydride complexes acting both as a reducing agent and precursor for Cu ALD - A study through Density Functional Theory Gangotri Dey · Simon D. Elliott the date of receipt and acceptance should be inserted later Abstract We propose dual functional copper complexes that may act both as reducing agents and as Cu sources for prospective Cu Atomic Layer Deposition (ALD). Here we see a CuH carbene complex, which can donate the H- anion to another Cu precursor forming neu- tral by-products and metallic Cu(0).
    [Show full text]
  • The Synthesis of Novel Aryl and Alkyl Phosphine-Imidazolium Salts
    The Synthesis of Novel Aryl and Alkyl Phosphine-Imidazolium Salts by Huw John Roberts B.Sc. (Hons) This thesis is presented for the degree of Doctor of Philosophy to the University of Wales Cardiff, Department of Chemistry 2007 The work described in this thesis was carried out in the Department of Chemistry at the University of Wales Cardiff under the supervision of Prof. Kingsley J. Cavell UMI Number: U585058 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Dissertation Publishing UMI U585058 Published by ProQuest LLC 2013. Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 Declaration DECLARATION This work has not previously been accepted in substance for any degree and is not concurrently submitte submitted in candidature for any degree.currently Signed (candidate) Date ............... STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree o f .................... (insert MCh, MD, MPhil, PhD etc, as appropriate) Signed ........................................ (candidate) D ate *>.}.?. J M ............. STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated. Other sources are acknowledged by explicit references.
    [Show full text]
  • Preparatory Problems Preparatory • Icho 44 Icho Preparatory Problems
    Preparatory Problems • IChO 44 Preparatory Problems 44th International Chemistry Olympiad July 21–30, 2012 United States of America Preparatory Problems IChO 2012 Preparatory Problems with Working Solutions 44th International Chemistry Olympiad Co-Editors: Michael P. Doyle and Andrei N. Vedernikov Department of Chemistry and Biochemistry University of Maryland at College Park Tel: 001 301 405 1788; Fax: 001 301 314 2779 Email: [email protected] November 2011 Published 2011 American Chemical Society All rights reserved Commercial sale is prohibited Preparatory Problems IChO 2012 Contributing Authors Seth N. Brown, University of Notre Dame Michael P. Doyle, University of Maryland Daniel E. Falvey, University of Maryland George R. Helz, University of Maryland Kaveh Jorabchi, Georgetown University Douglas A. Julin, University of Maryland J.L. Kiappes, University of Oxford John Kotz, State University of New York Evguenii Kozliak, University of North Dakota Amy S. Mullin, University of Maryland Garegin A. Papoian, University of Maryland Elena Rybak-Akimova, Tufts University Andrei N. Vedernikov, University of Maryland 2 Preparatory Problems IChO 2012 Preface We are happy to provide Preparatory Problems for the 44th International Chemistry Olympiad. These problems were prepared with reliance on fundamental topics that are traditionally covered in high school chemistry courses supplemented with six topics of advanced difficulty for the Theoretical part and one topic of advanced difficulty for the Practical part. These topics are listed under “Topics of Advanced Difficulty”, and their applications are given in the problems. In our experience each of these topics can be introduced in two to three hours. Whenever possible the relevance of the problem in the chemical sciences, and to the complex world in which we live, is given.
    [Show full text]
  • Chapter 1 Small Molecule Activation by Main
    VU Research Portal Small Molecule Activation and Capture by Preorganized Frustrated Lewis Pairs Bertini, F. 2013 document version Publisher's PDF, also known as Version of record Link to publication in VU Research Portal citation for published version (APA) Bertini, F. (2013). Small Molecule Activation and Capture by Preorganized Frustrated Lewis Pairs. General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. E-mail address: [email protected] Download date: 02. Oct. 2021 Chapter 1 Small Molecule Activation by Main Group Compounds Federica Bertini, J. Chris Slootweg, Koop Lammertsma Abstract: This introductory chapter describes recent spectacular discoveries with respect to the new and fascinating field of small molecule activation by main group compounds. Chapter 1 1.11.11.1.1.1 ... IIIntroductionIntroduction The activation of small molecules like H 2, CO 2, NH 3, P 4 and N 2O among others, and their subsequent utilization for synthetic purposes, is of fundamental importance in chemistry.
    [Show full text]
  • 1949 N-Heterocyclic Carbene Ligands and Their Rh(I)
    1949 N-Heterocyclic carbene ligands and their Rh(I) complexes Mechanochemical and solvent synthesis and catalytic applications PhD thesis Sourav De Supervisor: Dr. Ferenc Joó UNIVERSITY OF DEBRECEN Doctoral Council of Natural Sciences and Information Technology Doctoral School of Chemistry Debrecen, 2020. Declaration I, Sourav De, have prepared This Dissertation within the Reaction Kinetics and Catalysis (K/1) Program of the Doctoral School of Chemistry of the Doctoral Council of Natural Sciences and Information Technology of the University of Debrecen with the aim of obtaining the Doctor of Philosophy (PhD) degree in Sciences from the University of Debrecen. Herewith I declare, that the results included in This Dissertation are not included in other PhD dissertation(s). Debrecen, 2020 ……..... ……………………………………… Signature of the applicant Herewith I, Ferenc Joó, attest that the applicant, Sourav De has carried out his research in the period of 2016-2020 under my supervision within the Reaction Kinetics and Catalysis (K/1) Program of the Doctoral School of Chemistry. With his independent and ingenious research activity, the applicant made decisive contributions to the results contained in This Dissertation. Herewith I declare, that the results included in This Dissertation are not included in other PhD dissertation(s). I recommend the approval of the Dissertation. Debrecen, 2020 …....…. ………………………………………….. Signature of the supervisor N-Heterocyclic carbene ligands and their Rh(I) complexes Mechanochemical and solvent synthesis and catalytic applications Dissertation submitted in partial fulfilment of the requirements for the doctoral degree (PhD) in Chemistry Written by Sourav De (MSc in Chemistry) Prepared in the framework of the Doctoral School of Chemistry of the University of Debrecen (K/1 Reaction Kinetics and Catalysis programme) Dissertation advisor: Dr.
    [Show full text]
  • Supported Au Nanoparticles with N-Heterocyclic Carbene Ligands As
    Article Cite This: J. Am. Chem. Soc. 2018, 140, 4144−4149 pubs.acs.org/JACS Supported Au Nanoparticles with N‑Heterocyclic Carbene Ligands as Active and Stable Heterogeneous Catalysts for Lactonization † ‡ ⊥ ¶ # † # † § ∥ Rong Ye, , , , , Aleksandr V. Zhukhovitskiy, , Roman V. Kazantsev, , Sirine C. Fakra, † † ‡ † ‡ ⊥ Brent B. Wickemeyer, F. Dean Toste,*, , and Gabor A. Somorjai*, , , † ⊥ Department of Chemistry, Kavli Energy NanoScience Institute, University of California, Berkeley, Berkeley, California 94720, United States ‡ § ∥ Chemical Science Division, Joint Center for Artificial Photosynthesis, Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States *S Supporting Information ABSTRACT: Attachment of N-heterocyclic carbenes (NHCs) on the surface of metal nanoparticle (NP) catalysts permits fine-tuning of catalytic activity and product selectivity. Yet, NHC-coated Au NPs have been seldom used in catalysis beyond hydrogenation chemistry. One challenge in this field has been to develop a platform that permits arbitrary ligand modification without having to compromise NP stability toward aggregation or leaching. Herein, we exploit the strategy of supported dendrimer-encapsulated metal clusters (DEMCs) to achieve aggregation-stable yet active heterogeneous Au NP catalysts with NHC ligands. Dendrimers function as aggregation-inhibitors during the NP synthesis, and NHCs, well-known for their strong attachment to the gold surface, provide a handle to modify the stereochemistry, stereoelectronics, and chemical functionality of the NP surface. Indeed, compared to “ligandless” Au NPs which are virtually inactive below 80 °C, the NHC-ligated Au NP catalysts enable a model lactonization reaction to proceed at 20 °C on the same time scale (hours). Based on Eyring analysis, proto-deauration is the turnover-limiting step accelerated by the NHC ligands.
    [Show full text]
  • Synthesis and Reactivity of Transition Metal and Main Group Hydrogenation Catalysts
    Synthesis and Reactivity of Transition Metal and Main Group Hydrogenation Catalysts by Eliar Mosaferi A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemistry University of Toronto © Copyright by Eliar Mosaferi 2019 Synthesis and Reactivity of Transition Metal and Main Group Hydrogenation Catalysts Eliar Mosaferi Doctor of Philosophy Department of Chemistry University of Toronto 2019 Abstract Since its discovery by Paul Sabatier, catalytic hydrogenation of unsaturated substrates has become the single largest industrial process to date and encompasses the production of many products, such as foods, agrochemicals, pharmaceuticals, and materials. Over the last century research in the area has predominantly focused on the use of transition metals such as palladium, platinum, rhodium, and ruthenium to develop heterogeneous and homogeneous hydrogenation catalysts. The research presented herein focuses on the use of ruthenium complexes bearing electron-rich phosphorylated N-heterocyclic carbene ligands as well as the development of main- group compounds for frustrated Lewis pair catalysis. Complexes [Ru(0)LL’2(CO)] and [RuHL2(CO)][Cl], where L = N-phosphorylated N- heterocyclic carbene (NHCP), and L’ = triphenylphosphine, were prepared as a mixture by treatment of RuHCl(CO)(PPh3)3 with excess NHCP carbene and separated by crystallization. The zero-valent complex [Ru(0)LL’2(CO)] was shown to undergo rapid oxidative addition to the corresponding Ru(II) species when treated with small molecules to afford complexes of the general type [RuHXLL’(CO)], where L = N-phosphorylated N-heterocyclic carbene, L = triphenylphosphine, and X = H, SiPh3, or Si(H)Ph2. ii The reaction of NHCP carbene with [RuCl2(p-cymene)]2 resulted in the isolation of the piano- stool half-sandwich complex [RuCl2(p-cymene)(NHCP)] as well as an unusual arene-activated species.
    [Show full text]