DOCSLIB.ORG

Bis(N-Heterocyclic Carbene)Carbazolide Pincer Complexes of S- and P-Block Metals and Related Studies

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Bis(N-Heterocyclic Carbene)Carbazolide Pincer Complexes of S- and P-Block Metals and Related Studies AUSTRALIA Bis(N-Heterocyclic Carbene)Carbazolide Pincer Complexes of s- and p-Block Metals and Related Studies A thesis in partial fulfilment of the requirements for the degree of Doctor of Philosophy (Chemistry) by Kai N. Buys Supervisor: Assoc. Prof. Marcus L. Cole School of Chemistry The University of New South Wales Sydney, Australia April 2017 THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: BUYS First name: KAI Other name/s: NICHOLAS Abbreviation for degree as given in the University calendar: PhD School: CHEMISTRY Faculty: SCIENCE Title: Bis(N Heterocyclic Carbene)Carbazolide Pincer Complexes of s- and p-Block Metals and Related Studies Abstract 350 words maximum: This work presents synthetic investigations into main group organometallic chemistry, placing particular emphasis on the study of bis-N-heterocyclic carbene (NHC) carbazolide coordination environments. Complexes of high and low oxidation state metals from the s- and p-blocks were targeted and these comprise the content of the experimental chapters two through five. Chapter one serves as a general introduction to rationalise the intent of this work. Herein focus is drawn to the nascent field of organometallic main group chemistry in the form of a discussion of its history using pertinent recent examples from the literature. Chapter two details the synthesis of an emerging class of versatile bis(NHC)carbazolide pincer ligands; bimcaR, and their complexation to s-block metals. The development of a new zwitterionic bis(imidazolium)carbazolide proligand is discussed, as well as the structural metrics of new lithium and magnesium bimcaR derivatives. Specifically, a new iodomagnesium complex is probed for its synthetic utility as a ligand-transfer agent and catalytic precursor in conjunction with attempts to access a reduced Mg(I) derivative. Chapter three focuses on the stabilising effect of the flanking bis(NHC) moieties of bimcaR on high valent group 13 metals and thusly presents a series of exceptionally stable bimcaR supported diiodides from aluminium to thallium. The indium- and thallium diiodides are subjected to iodide- hydride exchange reactions to assess the stability of the resulting dihydrides, whilst efforts are also made to access low valent heavy group 13 congeners. Chapter four concentrates on the extension of this methodology to accessing heavy low valent group 14 complexes with the aim of creating highly activated metal centres to harness main group redox chemistry. To this end, a number of attempts are made to access low valent tin and lead halides with a view toward accessing the corresponding, highly reactive metallohydrides. Chapter five presents an alternative approach to accessing such reactive group 14 species with the bulky triazenide ligand class, and thereby details the synthesis and steric characterisation of a new super bulky, unsymmetrical N-2,6-terphenyl triazenide ligand. Declaration relating to disposition of project thesis/dissertation I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only). …………………………………………………………… ……………………………………..……………… ……….……………………...…….… Signature Witness Signature Date The University recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: Originality Statement ‘I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged.’ Signed …………………………………………………. Date …………………………………………………. COPYRIGHT STATEMENT ‘I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; where permission has not been granted I have applied/will apply for a partial restriction of the digital copy of my thesis or dissertation.' Signed ……………………………………………........................... Date ……………………………………………........................... AUTHENTICITY STATEMENT ‘I certify that the Library deposit digital copy is a direct equivalent of the final officially approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format.’ Signed ……………………………………………........................... Date ……………………………………………........................... Acknowledgments My biggest expression of gratitude must go to my supervisor, Marcus Cole, who was always supportive of my work - through thick and thirsty - and in his own way, he has kindly taught me some of life’s valuable lessons. Specifically, I must thank him for his patience and guidance in teaching me the delicate arts of wordsmithing and single crystal X-ray diffraction. With regard to the latter, I would also like to acknowledge Mohan Bhadbhade for his uncanny expertise in taming the machine spirits of our, at times, temperamental diffractometer. To all the residents of the 1003 laboratory, please accept my humble thanks for creating such an animated workplace. Christoph, Pete, Tom, Skimmo, Niamh, and Kirsty, you have exceptional tastes in lifestyle! Sam, know that your help throughout my project was invaluable, especially when I was but a young pup (and thanks for all the free stuff). I am equally thankful for the truly special opportunity to visit Doris Kunz and her research group at the University of Tübingen. My stay was made all the better by her friendly group members. Special mentions go to Bucki, Eva, Therry, and Domme for welcoming me into their extracurricular mischiefs and odd traditions. Of course, none of this work would have been possible without the unwavering love of my dear friends and family at home: Pig, Jay, G, and obviously the members of the Super Deluxe Dream Team; Bunk, Bogdan, Thud, and Spicy. Many of you I have known since my very beginning, may we have countless more floats and quick pumps. Mama and Pops, your ceaseless support often materialised as food and coffee donations, these were always welcome, especially towards the end. Brother dearest, sorry for eating your food during my times of need. Finally, I would like to thank you, the kind reader, for at least making it this far. Great job! Table of Contents Abstract ........................................................................................................................... vii List of abbreviations ...................................................................................................... viii List of Compounds ......................................................................................................... xv Chapter 1 – General Introduction ................................................................................... 1 1.1 Introduction to main group organometallics .......................................................... 1 1.2 Introduction to p-block organometallics ................................................................. 2 1.2.1 Monoanionic ligands ........................................................................................ 6 1.2.2 The “Gallyne” debate ....................................................................................... 7 1.3 Heavy p-block metallohydrides ............................................................................... 9 1.4 Introduction to s-Block organometallics ............................................................... 12 1.4.1 1,8-Disubstituted carbazolides as support ligands ......................................... 13 1.4.2-Diketiminates
Load more

Recommended publications
  • Triazene (H2NNNH) Or Triimide (HNHNNH) Markofçrstel,[A, D] Yetsedaw A
    DOI:10.1002/cphc.201600414 Articles On the Formation of N3H3 Isomers in Irradiated Ammonia Bearing Ices:Triazene (H2NNNH) or Triimide (HNHNNH) MarkoFçrstel,[a, d] Yetsedaw A. Tsegaw,[b] Pavlo Maksyutenko,[a, d] Alexander M. Mebel,[c] Wolfram Sander,[b] and Ralf I. Kaiser*[a, d] The remarkable versatility of triazenesinsynthesis, polymer theoretical studies with our novel detection scheme of photo- chemistry and pharmacology has led to numerousexperimen- ionization-driven reflectron time-of-flight mass spectroscopy tal and theoretical studies.Surprisingly,only very little is we can obtain information on the isomersoftriazene formed known aboutthe most fundamental triazene:the parentmole- in the films. Using isotopically labeled starting material, we can cule with the chemical formula N3H3.Here we observe molecu- additionally gain insightinthe formation pathways of the iso- lar,isolated N3H3 in the gas phase after it sublimes from ener- mers of N3H3 under investigation and identify the isomers getically processed ammonia and nitrogen films. Combining formedastriazene (H2NNNH) andpossibly triimide(HNHNNH). 1. Introduction During the last decades, triazenes—a class of organic mole- life time of at least 1mswas also inferred as an intermediate cules carrying the =N N=N moiety—have received substan- in the radiolysis of an aqueous solution of hydrazine based on À À tial attention both from the theoretical and organic chemistry asingle absorption feature at 230 nm.[6] The cyclic isomer of [1] communities. Derived from cis-and trans-triazene (HN=NNH2 ; triazene, cyclotriazane, was first reported crystallographically in Scheme1), the substituted counterparts have significant appli- zeolite A, where it was stabilized by asilver cation as [1a,c] [1d] + [7] + cations in synthetic chemistry, polymer science, and phar- Ag(N3H3) .
    [Show full text]
  • Studies on New Vasodilators, Ws-1228 a and B Ii. Structure and Synthesis
    VOL. XXXV NO. 2 THE JOURNAL OF ANTIBIOTICS 157 STUDIES ON NEW VASODILATORS, WS-1228 A AND B II. STRUCTURE AND SYNTHESIS HIROKAZU TANAKA, KEIZO YOSHIDA, YOSHIKUNI ITOH and HIROSHI IMANAKA Fermentation Research Laboratories, Fujisawa Pharmaceutical Co., Ltd., Osaka, Japan (Received for publication October 26, 1981) The structure of new hypotensive vasodilators, WS-1228 A and B, produced by Strepto- myces aureofaciens, were determined as I and 2, respectively, on the basis of their spectral and chemical evidences. WS-1228 A (1), having N-hydroxytriazene moiety, was synthesized from (E,E,E)-2,4,7- undecatrienal (4) by condensation with hydrazine hydrate followed by nitrosation. In the course of screening for new biologically active compounds, we found that Streptomyces aureofaciens produces hypotensive vasodilators designated as WS-1228 A (1) and B (2). Taxonomy, isolation and characterization of these compounds have been reported in the preceding papery. This report describes the structure elucidations of WS-1228 A (1) and B (2) and the synthesis of 1. WS-1228 A (1) WS-1228 B (2) WS-1228 A (1) was isolated as yellow needles [mp 100 - 102°C (dec.)] which showed a positive color reaction to ferric chloride reagent. Elemental analysis and mass spectrum established the molecular formula of 1 as C11H17N3O. Absorption bands at 1612 and 1580 cm-1 in its IR spectrum (Fig. 1) and at 300 nm in its UV spectrum suggested the presence of the triene oxime moiety. The PMR spectrum (Fig. Fig. 1. IR spectrum of WS-1228 A (1) (Nujol). 158 THE JOURNAL OF ANTIBIOTICS FEB.
    [Show full text]
  • The Road Travelled: After Main‐Group Elements As Transition Metals
    ChemCatChem 10.1002/cctc.201800963 MINIREVIEW The Road Travelled: After Main-group Elements as Transition Metals Catherine Weetman and Shigeyoshi Inoue* Dedicated to Professor Philip Power on the occasion of his 65th birthday Manuscript Accepted This article is protected by copyright. All rights reserved. ChemCatChem 10.1002/cctc.201800963 CONCEPT The Road Travelled: After Main-group Elements as Transition Metals Catherine Weetman and Shigeyoshi Inoue* Dedicated to Professor Philip Power on the occasion of his 65th birthday Abstract: Since the latter quarter of the twentieth century, main group conditions. This was rationalised due to main group species chemistry has undergone significant advances. Power’s timely review possessing donor/acceptor frontier orbitals which are separated in 2010 highlighted the inherent differences between the lighter and by modest energy gaps, thus drawing comparisons to open-shell heavier main group elements, and that the heavier analogues transition metal species. resemble transition metals as shown by their reactivity towards small In the last 10 years since the landmark review, main group molecules. In this concept article, we present an overview of the last chemistry has continued to flourish. Frustrated Lewis Pair (FLP) 10 years since Power’s seminal review, and the progress made for chemistry has been widely established since the pioneering work catalytic application. This examines the use of low-oxidation state of Stephan.[7] Many more donor/acceptor combinations of main- and/or low-coordinate group 13 and 14 complexes towards small group elements have been isolated (as predicted by Power[1]) and molecule activation (oxidative addition step in a redox based cycle) have led to a variety of new reactions through new mechanistic and how ligand design plays a crucial role in influencing subsequent pathways.[8] For example, the use of phosphonium cations have reactivity.
    [Show full text]
  • Condensed-Phase Photochemistry in the Absence of Radiation Chemistry Ella Mullikin
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Wellesley College Wellesley College Wellesley College Digital Scholarship and Archive Faculty Research and Scholarship 6-27-2018 Condensed-Phase Photochemistry in the Absence of Radiation Chemistry Ella Mullikin Pierce van Mulbregt Jeniffer Perea Muhammad Kasule Jean Huang See next page for additional authors Follow this and additional works at: https://repository.wellesley.edu/scholarship Version: Post-print Recommended Citation E. Mullikin, P. van Mulbregt, J. Perea, M. Kasule, J. Huang, C. Buffo, J. Campbell, L. Gates, H. M. Cumberbatch, Z. Peeler, H. Schneider, J. Lukens, S. T. Bao, R. Tano-Menka, S. Baniya, K. Cui, M. Thompson, A. Hay, L. Widdup, A. Caldwell-Overdier, J. Huang, M. C. Boyer, M. Rajappan, G. Echebiri and C. R. Arumainayagam, ACS Earth and Space Chemistry, 2018, DOI: 10.1021/ acsearthspacechem.8b00027. This Article is brought to you for free and open access by Wellesley College Digital Scholarship and Archive. It has been accepted for inclusion in Faculty Research and Scholarship by an authorized administrator of Wellesley College Digital Scholarship and Archive. For more information, please contact [email protected]. Authors Ella Mullikin, Pierce van Mulbregt, Jeniffer Perea, Muhammad Kasule, Jean Huang, Christina Buffo, Jyoti Campbell, Leslie Gates, Helen M. Cumberbatch, Zoe Peeler, Hope Schneider, Julia Lukens, Si Tong Bao, Rhoda Tano-Menka, Subha Baniya, Kendra Cui, Mayla Thompson, Aury Hay, Lily Widdup, Anna Caldwell- Overier, Justine Huang, Michael C. Boyer, Mahesh Rajappan, Geraldine Echebiri, and Christopher R. Arumainayagam This article is available at Wellesley College Digital Scholarship and Archive: https://repository.wellesley.edu/scholarship/183 Condensed-Phase Photochemistry in the Absence of Radiation Chemistry Ella Mullikin,1 Pierce van Mulbregt,2 Jeniffer Perea,1 Muhammad Kasule,3 Jean Huang,1 Christina Buffo,1 Jyoti Campbell,1 Leslie Gates,1 Helen M.
    [Show full text]
  • Recent Progress in the Development of Multitasking Directing Groups for Carbon–Hydrogen Activation Reactions
    SYNLETT0936-52141437-2096 © Georg Thieme Verlag Stuttgart · New York 2015, 26, 2751–2762 2751 account Syn lett H. Sun, Y. Huang Account Recent Progress in the Development of Multitasking Directing Groups for Carbon–Hydrogen Activation Reactions Huan Sun Yong Huang* Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University, Shenzhen Graduate School, Shenzhen 518055, P. R. of China [email protected] Received: 17.05.2015 hydrogen bond (Scheme 1). This property enables the DG to Accepted after revision: 15.07.2015 govern the site selectivity of carbon–hydrogen functional- Published online: 07.09.2015 DOI: 10.1055/s-0035-1560169; Art ID: st-2015-a0376-a ization reactions. Many DGs, ranging from strongly chelating to weakly Abstract Selective carbon–hydrogen activation reactions can be ac- binding, have been developed for a wide range of carbon– complished in a predictive manner using directing auxiliaries. However, hydrogen coupling and annulation reactions.3 However, it the majority of directing groups discovered to date are difficult to re- move or to transform into a desirable functionality. Recently, remov- must be pointed out that this approach is a double-edged able, cleavable, and redox-neutral directing groups have been devel- sword because although it provides precise site selectivity, oped that significantly broaden both the substrate scope and synthetic it suffers from the fact that the DG remains as a functional diversity of carbon–hydrogen functionalization reactions. In this short entity in the product of the reaction. For example, DGs for account, we summarize recent progress we have made in the develop- 2 ment of multitasking (removable, cleavable, redox-neutral, manipula- sp -carbon–hydrogen functionalization reactions are typi- ble) directing groups for carbon–hydrogen activation reactions.
    [Show full text]
  • A Thesis Presented by in Partial Fulfillment of Requirements for The
    1 NEW AROMATIC FLUORINATIONS A Thesis Presented by LOUIS JOSEPH DIORAZIO in partial fulfillment of requirements for the degree of Doctor of Philosophy of the UNIVERSITY of LONDON Alan Johnson Laboratory Department of Chemistry IMPERIAL COLLEGE LONDON SW7 2AY September 1991 To Mum and Dad 2 Abstract This thesis is divided into four parts. The first two Chapters offer a review of the field of aromatic fluorination from 1980 until June 1991. The reactions studied are divided into two groups, those based on nucleophilic fluorination (Chapter one, Fluoride ion-based methodology) and those using electrophilic reactions (Chapter two, Molecular fluorine and reagents derived from this). Mention is made throughout of methods used in radiolabelling studies with the unstable isotope, fluorine-18. In the third Chapter, the development of a method for producing regioselective fluoroaromatics based on the fluorodemetallation process is discussed. The reagent used in this study was the electrophilic, fluorinating agent, caesium fluoroxysulphate, which was readily prepared in multigram quantities from molecular fluorine. The variation of the metalloid leaving group from the initial choice of silicon through to boron is discussed and the investigation of the role of the ligands surrounding the metal is rationalised. An hypothesis is presented to explain the different results seen in various solvents. This proposes the formationin situ of new fluorinating agents by reaction of caesium fluoroxysulphate with solvent molecules. Of the solvents investigated, methanol was found to give the most rapid reaction with a number of tricoordinate arylboron compounds. This was attributed to the formation of methyl hypofluorite whose reactivity was mediated by adduct formation with the substrate.
    [Show full text]
  • Large Intermediates in Hydrazine Decomposition: a Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces
    Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Grinberg Dana, Alon et al. "Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N₃H₅ and N₄H₆ Potential Energy Surfaces." Journal of Physical Chemistry A 123, 22 (May 2019): 4679-4692 © 2019 American Chemical Society As Published http://dx.doi.org/10.1021/acs.jpca.9b02217 Publisher American Chemical Society (ACS) Version Author's final manuscript Citable link https://hdl.handle.net/1721.1/124015 Terms of Use Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. The Journal of Physical Chemistry This document is confidential and is proprietary to the American Chemical Society and its authors. Do not copy or disclose without written permission. If you have received this item in error, notify the sender and delete all copies. Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the N3H5 and N4H6 Potential Energy Surfaces Journal: The Journal of Physical Chemistry Manuscript ID jp-2019-02217p.R1 Manuscript Type: Article Date Submitted by the n/a Author: Complete List of Authors: Grinberg Dana, Alon; Massachusetts Institute of Technology, Chemical Engineering Moore, Kevin; Argonne National Laboratory, Gas Phase Chemical Dynamics Jasper, Ahren; Argonne National Laboratory, Gas Phase Chemical Dynamics Green, William; Massachusetts Institute of Technology, Chemical Engineering ACS Paragon Plus Environment Page 1 of 60 The Journal of Physical Chemistry 1 2 3 4 5 Large Intermediates in Hydrazine Decomposition: A Theoretical Study of the 6 7 N3H5 and N4H6 Potential Energy Surfaces 8 9 1 2 2 1 10 Alon Grinberg Dana , Kevin B.
    [Show full text]
  • Precursor Chemistry of Novel Metal Triazenides : Solution and Vapor Phase Elaborations of Fe and Al13fe4 Nanomaterials Khaled Soussi
    Precursor chemistry of novel metal triazenides : Solution and vapor phase elaborations of Fe and Al13Fe4 nanomaterials Khaled Soussi To cite this version: Khaled Soussi. Precursor chemistry of novel metal triazenides : Solution and vapor phase elabo- rations of Fe and Al13Fe4 nanomaterials. Catalysis. Université de Lyon, 2017. English. NNT : 2017LYSE1006. tel-01513076 HAL Id: tel-01513076 https://tel.archives-ouvertes.fr/tel-01513076 Submitted on 24 Apr 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. No d’ordre NNT : 2017LYSE1006 THÈSE DE DOCTORAT DE L’UNIVERSITÉ DE LYON opérée au sein de l’Université Claude Bernard Lyon 1 École Doctorale ED206 Chimie, Procédés, Environnement Spécialité de doctorat : Chimie Discipline : Chimie Soutenue publiquement le 27/01/2017, par : Khaled Soussi Precursor chemistry of novel metal triazenides : Solution and vapor phase elaborations of Fe and Al13Fe4 nanomaterials Devant le jury composé de : Mme. Catherine Santini, Directeur de Recherche, CPE Lyon Présidente M. Franck Denat, Professeur, Université de Bourgogne Rapporteur Mme. Elisabeth Blanquet, Directrice de Recherche, INP Grenoble Rapporteur M. Constantin Vahlas, Directeur de Recherche, CIRIMAT Toulouse Examinateur M. Christophe Darcel, Professeur, Université de Rennes1 Examinateur Mme. Amandine Cabiac, Ingénieur de recherche, IFP Energies nouvelles Examinatrice M.
    [Show full text]
  • Comparison of the Thermal Stabilities of Diazonium Salts and Their
    Comparison of the thermal stability of diazonium salts and their corresponding triazenes Christiane Schotten1,2, Samy K. Leprevost1, Low Ming Yong1, Colan E. Hughes1, Kenneth D. M. Harris1, Duncan L. Browne1,3* 1School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, UK 2 School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, England, UK 3 School of Pharmacy, University College London, 29-39 Brunswick Square, London WC1N 1AX, England, UK 1 ABSTRACT A range of diazonium salts and their corresponding triazenes have been prepared in order to directly compare their relative thermal stabilities (via initial decomposition temperature) from differential scanning calorimetry (DSC) data. A structure-stability relationship (SSR) has been explored to investigate trends in stability, depending on the aromatic substituent and the structure of the secondary amine component of the diazonium salts and triazenes. All triazenes investigated show significantly greater stability (in many cases stable above 200 °C) compared to the corresponding diazonium salts, which show varying stabilities. KEYWORDS triazene, diazonium salt, thermal stability, DSC, continuous processing INTRODUCTION Diazonium salts are important intermediates in synthetic chemistry as they permit functionalization or transformation at the attached aromatic carbon. Consequently, many transformations utilizing diazonium salts have been developed.1-3 However, variability in the stability of diazonium salts renders their use at large scale problematic.4, 5 The stability of diazonium salts ranges from excellent to explosive, though very few are in the latter category. Nonetheless, the existence of some explosive compounds raises caution and concern, which provides motivation for the development of alternative synthetic route design to avoid diazonium salt chemistry.
    [Show full text]
  • Structures, Energies, and Bonding Analysis of Monoaurated Complexes with N-Heterocyclic Carbene and Analogues T.A.N
    ASEAN J. Sci. Technol. Dev., 32(1): 1 – 15 Structures, Energies, and Bonding Analysis of Monoaurated Complexes with N-Heterocyclic Carbene and Analogues T.A.N. NGUYEN1*, T.P.L. HUYNH1, T.X.P. VO1, T.H. TRAN1, D.S. TRAN2, T.H. DANG3 AND T.Q. DUONG4 In this work, we computationally investigated from quantum chemical calculations (DFT) at the BP86 level with the various basis sets def2-SVP, def2-TZVPP, and TZ2P+, chemical bonding issues of the recently described carbene-analogues gold(I) complexes AuCl-NHEMe (Au1-NHE) with E = C – Pb. The optimized structures and the metal-ligand bond dissociation energy (BDE) were calculated, and the nature of the E→Au bond was studied with charge and energy decomposition methods. The equilibrium structures of the system showed that there were major differences in the bonded orientation from the ligands NHC-NHPb to gold(I) complex between the lighter and the heavier homologues. The BDEs results showed that the metal-carbene analogues bonds were very strong bonds and the strongest bond was calculated for Au1-NHC which had the bond strength De = 79.2 kcal/mol. Bonding analysis of Au1-NHE showed that NHE ligands exhibited donor- acceptor bonds with the σ lone pair electrons of NHE donated into the vacant orbital of the acceptor fragment (AuCl). The EDA-NOCV results indicated that the ligand NHE in Au1-NHE complexes were strong σ-donors and very weak π donor and the bond order in complexes was Au1-NHC > Au1-NHSi > Au1-NHGe > Au1-NHSn > Au1-NHPb. We also realised that the gold-ligand bond was characterized by a π back-donation component from the Au to the ligand.
    [Show full text]
  • Download PDF 1.71 MB
    The Dynamics of Electron-Induced Formation of N-2 and N-3 Species from Condensed Ammonia Jane L. Zhu Advisor: Christopher R. Arumainayagam, Ph.D. Department of Chemistry, Wellesley College Submitted in Partial Fulfillment of the Prerequisites for Honors in Chemistry April 2016 © Jane L. Zhu i Acknowledgements First and foremost, I have nothing but the utmost thanks for my advisor, Chris Arumainayagam. You have taught me so much over the past four years. Thank you for always pushing me to be a better scholar and scientist. More importantly, thank you for believing in me. Thank you to my thesis committee – Professor Mala Radhakrishnan and Professor Carla Verschoor. Your constructive criticisms, advice, and encouragement have been tremendously helpful during this process, especially during some of the more frustrating and stressful times. Thank you also to Professor Ellen Hildreth for graciously agreeing to serve as my honors visitor. Many thanks to the incredible chemistry department and science center staff. Thank you Professor Paul Reisberg for your immense support over the last several years. Special thanks to George Dai, Larry Knowles, and John DeBolt – you all have been so gracious with your time and efforts, especially when problems arose with our ultrahigh vacuum chamber. I would also like to thank my brilliant lab mates. Without you all, this thesis would not have been possible. Thank you all for always being so willing to come into lab bright and early in the morning and staying until midnight to help me with experiments and data analysis. I will miss you all dearly. I also cannot overstate my gratitude for my former lab mates, Katie Shulenberger’14 and Katherine Tran’15, for starting this ammonia project.
    [Show full text]
  • Sub-90° Interligand Bond Angles in Heavier Group 14 Dichalcogenolates
    This is an electronic reprint of the original article. This reprint may differ from the original in pagination and typographic detail. Author(s): Rekken, Brian; Brown, Thomas; Fettinger, James; Lips, Felicitas; Tuononen, Heikki; Herber, Rolfe; Power, Philip Title: Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles Year: 2013 Version: Please cite the original version: Rekken, B., Brown, T., Fettinger, J., Lips, F., Tuononen, H., Herber, R., & Power, P. (2013). Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub- 90° Interligand Bond Angles. Journal of the American Chemical Society, 135(27), 10134-10148. https://doi.org/10.1021/ja403802a All material supplied via JYX is protected by copyright and other intellectual property rights, and duplication or sale of all or part of any of the repository collections is not permitted, except that material may be duplicated by you for your research use or educational purposes in electronic or print form. You must obtain permission for any other use. Electronic or print copies may not be offered, whether for sale or otherwise to anyone who is not an authorised user. Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles Brian D. Rekken,† Thomas M. Brown,† James C. Fettinger,† Felicitas Lips,† Heikki M. Tuononen,*,§ Rolfe H. Herber,*,‡ Philip P. Power*,† †Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California, 95616, USA ‡Racah Institute of Physics, Hebrew University of Jerusalem, 91904, Jerusalem, Israel §Department of Chemistry, University of Jyväskylä, P.O.
    [Show full text]