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Symmetry of Three-Center, Four-Electron Bonds†‡
Chemical Science EDGE ARTICLE View Article Online View Journal | View Issue Symmetry of three-center, four-electron bonds†‡ b a c Cite this: Chem. Sci., 2020, 11,7979 Ann Christin Reiersølmoen, § Stefano Battaglia, § Sigurd Øien-Ødegaard, Arvind Kumar Gupta, d Anne Fiksdahl,b Roland Lindh a and Mate Erdelyi *a All publication charges for this article ´ ´ ´ have been paid for by the Royal Society of Chemistry Three-center, four-electron bonds provide unusually strong interactions; however, their nature remains ununderstood. Investigations of the strength, symmetry and the covalent versus electrostatic character of three-center hydrogen bonds have vastly contributed to the understanding of chemical bonding, whereas the assessments of the analogous three-center halogen, chalcogen, tetrel and metallic s^-type long bonding are still lagging behind. Herein, we disclose the X-ray crystallographic, NMR spectroscopic and computational investigation of three-center, four-electron [D–X–D]+ bonding for a variety of cations (X+ ¼ H+,Li+,Na+,F+,Cl+,Br+,I+,Ag+ and Au+) using a benchmark bidentate model system. Formation of a three-center bond, [D–X–D]+ is accompanied by an at least 30% shortening of the D–X Received 11th April 2020 bonds. We introduce a numerical index that correlates symmetry to the ionic size and the electron Accepted 19th June 2020 affinity of the central cation, X+. Providing an improved understanding of the fundamental factors DOI: 10.1039/d0sc02076a Creative Commons Attribution 3.0 Unported Licence. determining bond symmetry on a comprehensive level is expected to facilitate future developments and rsc.li/chemical-science applications of secondary bonding and hypervalent chemistry. -
Actinide Ground-State Properties-Theoretical Predictions
Actinide Ground-State Properties Theoretical predictions John M. Wills and Olle Eriksson electron-electron correlations—the electronic energy of the ground state of or nearly fifty years, the actinides interactions among the 5f electrons and solids, molecules, and atoms as a func- defied the efforts of solid-state between them and other electrons—are tional of electron density. The DFT Ftheorists to understand their expected to affect the bonding. prescription has had such a profound properties. These metals are among Low-symmetry crystal structures, impact on basic research in both the most complex of the long-lived relativistic effects, and electron- chemistry and solid-state physics that elements, and in the solid state, they electron correlations are very difficult Walter Kohn, its main inventor, was display some of the most unusual to treat in traditional electronic- one of the recipients of the 1998 behaviors of any series in the periodic structure calculations of metals and, Nobel Prize in Chemistry. table. Very low melting temperatures, until the last decade, were outside the In general, it is not possible to apply large anisotropic thermal-expansion realm of computational ability. And DFT without some approximation. coefficients, very low symmetry crystal yet, it is essential to treat these effects But many man-years of intense research structures, many solid-to-solid phase properly in order to understand the have yielded reliable approximate transitions—the list is daunting. Where physics of the actinides. Electron- expressions for the total energy in does one begin to put together an electron correlations are important in which all terms, except for a single- understanding of these elements? determining the degree to which 5f particle kinetic-energy term, can be In the last 10 years, together with electrons are localized at lattice sites. -
Which Pnictogen Is Best?† Cite This: New J
NJC PAPER Pnictogen bonding with alkoxide cages: which pnictogen is best?† Cite this: New J. Chem., 2019, 43,14305 Henry J. Trubenstein, ‡ Shiva Moaven, ‡ Maythe Vega, Daniel K. Unruh and Anthony F. Cozzolino * Pnictogen bonding is beginning to emerge as a useful supramolecular interaction. The design strategies for these systems are still in the early stages of development and much attention has been focused on the lighter pnictogens. Pnictogen bond donors can have up to three independent sites for binding which can result in triple pnictogen bonding. This has been observed in the self-assembly of antimony alkoxide cages, but not with the lighter congeners. This work reports structural characterization of an analogous arsenic alkoxide cage that engages in a single pnictogen bond and synthetic explorations of Received 14th July 2019, the bismuth congener. DFT calculations are used to evaluate the differences between the structures. Accepted 13th August 2019 Ultimately the partial charge on the pnictogen and the energy of the pnictogen lone pair dictate the DOI: 10.1039/c9nj03648b strength, orientation and number of pnictogen bonds that these cages form. Antimony cages strike the best balance between strength and directionality, allowing them to achieve triple pnictogen bonding rsc.li/njc where the other congeners do not. Introduction or bismuth.15–23 Recently, antimony centred PnBs have been purposefully designed into molecules to actively direct the self- A pnictogen bond (PnB), in analogy to a halogen or chalcogen assembly of reversed bilayer vesicles,24 enable anion binding bond (XB/HaB or ChB), is ‘‘the net attractive interaction between with applications in sensing and transport,25–28 self-assembly an electrophilic region associated with a [pnictogen] atom in a complex architectures through triple pnictogen bonding29 and molecular entity [the PnB donor] and a nucleophilic region in allow for supramolecular catalysis.30 These applications rely on another, or the same, molecular entity [the PnB acceptor].’’1 the predictable formation of PnBs. -
Of the Periodic Table
of the Periodic Table teacher notes Give your students a visual introduction to the families of the periodic table! This product includes eight mini- posters, one for each of the element families on the main group of the periodic table: Alkali Metals, Alkaline Earth Metals, Boron/Aluminum Group (Icosagens), Carbon Group (Crystallogens), Nitrogen Group (Pnictogens), Oxygen Group (Chalcogens), Halogens, and Noble Gases. The mini-posters give overview information about the family as well as a visual of where on the periodic table the family is located and a diagram of an atom of that family highlighting the number of valence electrons. Also included is the student packet, which is broken into the eight families and asks for specific information that students will find on the mini-posters. The students are also directed to color each family with a specific color on the blank graphic organizer at the end of their packet and they go to the fantastic interactive table at www.periodictable.com to learn even more about the elements in each family. Furthermore, there is a section for students to conduct their own research on the element of hydrogen, which does not belong to a family. When I use this activity, I print two of each mini-poster in color (pages 8 through 15 of this file), laminate them, and lay them on a big table. I have students work in partners to read about each family, one at a time, and complete that section of the student packet (pages 16 through 21 of this file). When they finish, they bring the mini-poster back to the table for another group to use. -
Structures and Reactivity of Transition-Metal Compounds
STRUCTURES AND REACTIVITY OF TRANSITION-METAL COMPOUNDS FEATURING METAL-LIGAND MULTIPLE BONDS A Dissertation by ZHENGGANG XU Submitted to the Office of Graduate and Professional Studies of Texas A&M University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Chair of Committee, Michael B. Hall Committee Members, Roland E. Allen Robert R. Lucchese Simon W. North Head of Department, David H. Russell August 2014 Major Subject: Chemistry Copyright 2014 Zhenggang Xu ABSTRACT This dissertation presents the results from density functional theory (DFT) calculations on three major projects I have been working on over the past several years. The first system is focused on the structure and reactivity of a novel osmium silylyne compounds featuring an Os≡Si triple bond. NMR simulation confirmed the existence of this compounds and bonding analysis like NBO and ETS-NOCV proved its triple bond character. The structures of the [2+2] cyclo-addition product from silylyne and other small molecules (PhC≡CPh and P≡CtBu) were also determined from possible isomers by energetic results and NMR simulations. The cycloaddition reactions were found to be under kinetic control and steric effects should be a major reason for that. Furthermore, the geometric and electronic structures of the osmium silylyne analogues (M≡E, M = Ru and Os; E = Si, Ge and Sn) are studied computationally and their similarities and distinctions are discussed. Both the second and third systems are related to the formation of transition metal imido compound (M=NR). In the second system a cationic oxorhenium(V) complex reacts with a series of arylazides (N3Ar) to give cationic cis-rhenium(VII) oxo imido complexes. -
Asian Journal of Chemistry Asian Journal of Chemistry
Asian Journal of Chemistry; Vol. 28, No. 1 (2016), 116-120 ASIAN JOURNAL OF CHEMISTRY http://dx.doi.org/10.14233/ajchem.2016.19262 Theoretical Studies on Interaction Between CO2 Gas and Imidazolium-Type Organic Ionic Liquid Using DFT and Natural Bond Orbital Calculations 1,2,* SAIED M. SOLIMAN 1Department of Chemistry, Rabigh College of Science and Art, King Abdulaziz University, Jeddah, P.O. Box 344, Rabigh 21911, Saudi Arabia 2Department of Chemistry, Faculty of Science, Alexandria University, P.O. Box 426 Ibrahimia, 21525 Alexandria, Egypt *Corresponding author: Tel: +966 565450752; E-mail: [email protected]; [email protected] Received: 20 April 2015; Accepted: 31 July 2015; Published online: 5 October 2015; AJC-17557 The interaction between 4,5-dibromo-1-butyl-3-methylimidazolium trifluoromethanesulfonate; [DBBIM][TFMSO3] ionic liquid and CO2 gas has been studied using DFT calculations. With the help of natural bond orbital (NBO) analyses, the second order perturbation energies of the most interacting natural bond orbitals and natural atomic charges have been predicted by the density functional theory (DFT) computations at the X3LYP/6-31++G(d,p) level of theory. The natural charge calculations showed that in the ionic liquid-CO2 system, the [DBBIM][TFMSO3] ionic liquid is the electron donor while CO2 gas is an electron acceptor. Further stabilization of the imidazolium ring π-system is produced due to the interaction of the CO2 gas with the ionic liquid. The polarization of the C–O and S1–O3 bonds are affected significantly by such interactions. The charge decomposition (CDA) analysis revealed the strong interactions between the [DBBIM]+ and – [TFMSO3] ions of the ionic liquid and the weak interaction between the ionic liquid and the CO2 gas. -
Periodic Table of the Elements Notes
Periodic Table of the Elements Notes Arrangement of the known elements based on atomic number and chemical and physical properties. Divided into three basic categories: Metals (left side of the table) Nonmetals (right side of the table) Metalloids (touching the zig zag line) Basic Organization by: Atomic structure Atomic number Chemical and Physical Properties Uses of the Periodic Table Useful in predicting: chemical behavior of the elements trends properties of the elements Atomic Structure Review: Atoms are made of protons, electrons, and neutrons. Elements are atoms of only one type. Elements are identified by the atomic number (# of protons in nucleus). Energy Levels Review: Electrons are arranged in a region around the nucleus called an electron cloud. Energy levels are located within the cloud. At least 1 energy level and as many as 7 energy levels exist in atoms Energy Levels & Valence Electrons Energy levels hold a specific amount of electrons: 1st level = up to 2 2nd level = up to 8 3rd level = up to 8 (first 18 elements only) The electrons in the outermost level are called valence electrons. Determine reactivity - how elements will react with others to form compounds Outermost level does not usually fill completely with electrons Using the Table to Identify Valence Electrons Elements are grouped into vertical columns because they have similar properties. These are called groups or families. Groups are numbered 1-18. Group numbers can help you determine the number of valence electrons: Group 1 has 1 valence electron. Group 2 has 2 valence electrons. Groups 3–12 are transition metals and have 1 or 2 valence electrons. -
Techniques of Preparation and Crystal Chemistry of Transuranic Chalcogenides and Pnictides D
Techniques of preparation and crystal chemistry of transuranic chalcogenides and pnictides D. Damien, R. Haire, J. Peterson To cite this version: D. Damien, R. Haire, J. Peterson. Techniques of preparation and crystal chemistry of transuranic chalcogenides and pnictides. Journal de Physique Colloques, 1979, 40 (C4), pp.C4-95-C4-100. 10.1051/jphyscol:1979430. jpa-00218826 HAL Id: jpa-00218826 https://hal.archives-ouvertes.fr/jpa-00218826 Submitted on 1 Jan 1979 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. JOURNAL DE PHYSIQUE Colloque C4, supplément au n° 4, Tome 40, avril 1979, page C4-95 Techniques of preparation and crystal chemistry of transuranic chalcogenides and pnictides (*) D. A. Damien (**), R. G. Haire and J. R. Peterson (t) Transuranium Research Laboratory, Oak Ridge National Laboratory, Oak Ridge, TN 37830, U.S.A. Résumé. — La cristallochimie d'un certain nombre de chalcogénures et pnictures d'éléments transuraniens a été étudiée en utilisant les isotopes Am, Cm, Bk et Cf. Les composés ont été préparés par réaction directe du métal avec l'élément chalcogène ou pnictogène à température élevée. Les chalcogénures supérieurs ont été dissociés thermiquement pour donner des composés à stœchiométrie plus basse dont les sesquichalco- génures constituent la limite. -
Organometallic Pnictogen Chemistry
Institut für Anorganische Chemie 2014 Fakultät für Chemie und Pharmazie | Sabine Reisinger aus Regensburg, geb. Scheuermayer am 15.07.1983 Studium: Chemie, Universität Regensburg Abschluss: Diplom Promotion: Prof. Dr. Manfred Scheer, Institut für Anorganische Chemie Sabine Reisinger Die vorliegende Arbeit enthält drei Kapitel zu unterschiedlichen Aspekten der metallorganischen Phosphor- und Arsen-Chemie. Zunächst werden Beiträge zur supramolekularen Chemie mit 5 Pn-Ligandkomplexen basierend auf [Cp*Fe(η -P5)] und 5 i [Cp*Fe(η - Pr3C3P2)] gezeigt, gefolgt von der Eisen-vermittelten Organometallic Pnictogen Aktivierung von P4, die zu einer selektiven C–P-Bindungsknüpfung führt, während das dritte Kapitel die Verwendung von Phosphor Chemistry – Three Aspects und Arsen als Donoratome in mehrkernigen Komplexen mit paramagnetischen Metallionen behandelt. Sabine Reisinger 2014 Alumniverein Chemie der Universität Regensburg E.V. [email protected] http://www.alumnichemie-uniregensburg.de Aspects Three – Chemistry Pnictogen Organometallic Fakultät für Chemie und Pharmazie ISBN 978-3-86845-118-4 Universität Regensburg Universitätsstraße 31 93053 Regensburg www.uni-regensburg.de 9 783868 451184 4 Sabine Reisinger Organometallic Pnictogen Chemistry – Three Aspects Organometallic Pnictogen Chemistry – Three Aspects Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) der Fakultät für Chemie und Pharmazie der Universität Regensburg vorgelegt von Sabine Reisinger, geb. Scheuermayer Regensburg 2014 Die Arbeit wurde von Prof. Dr. Manfred Scheer angeleitet. Das Promotionsgesuch wurde am 20.06.2014 eingereicht. Das Kolloquium fand am 11.07.2014 statt. Prüfungsausschuss: Vorsitzender: Prof. Dr. Helmut Motschmann 1. Gutachter: Prof. Dr. Manfred Scheer 2. Gutachter: Prof. Dr. Henri Brunner weiterer Prüfer: Prof. Dr. Bernhard Dick Dissertationsreihe der Fakultät für Chemie und Pharmazie der Universität Regensburg, Band 4 Herausgegeben vom Alumniverein Chemie der Universität Regensburg e.V. -
Periodic Table Key Concepts
Periodic Table Key Concepts Periodic Table Basics The periodic table is a table of all the elements which make up matter Elements initially grouped in a table by Dmitri Mendeleev Symbols – each element has a symbol which is either a Capital Letter or a Capital Letter followed by a lower case letter Atomic Number – the number above an element’s symbol which shows the number of protons Atomic Mass – the number found below an elements symbol which shows the mass of the element. Mass = the number of protons + the number of neutrons Metals – the elements which have the properties of malleability, luster, and conductivity o These elements are good conductors of electricity & heat. o Found to the left of the zig-zag line on the periodic table Nonmetals – do not have the properties of metals. Found to the right of the zig-zag line Metalloids – elements found along the zig-zag line of the periodic table and have some properties of metals and nonmetals (B, Si, Ge, As, Sb, Te, and Po) Groups The columns going up and down (There are 18 groups) Group 1: Hydrogen, Lithium, Sodium, Potassium, Rubidium, Cesium, and Francium Elements arranged so that elements with similar properties would be in the same group. o Group 1 Alkali Metals - highly reactive metals o Group 2 Alkali Earth Metals – reactive metals o Group 3-12 Transition Metals o Group 17 Halogens – highly reactive non-metals o Group 18 Noble Gases - do not react or combine with any other elements. Elements are grouped according to their properties or reactivity Reactivity is determined by the number of electrons in an element’s outer energy level These electrons are called valence electrons Periods The rows that run from left to right on the periodic table (There are 7 periods) Period 1 contains 2 elements, Hydrogen and Helium. -
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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
3 Families of Elements
Name Class Date CHAPTER 5 The Periodic Table SECTION 3 Families of Elements KEY IDEAS As you read this section, keep these questions in mind: • What makes up a family of elements? • What properties do the elements in a group share? • Why does carbon form so many compounds? What Are Element Families? Recall that all elements can be classified into three READING TOOLBOX categories: metals, nonmetals, and semiconductors. Organize As you read Scientists classify the elements further into five families. this section, create a chart The atoms of all elements in most families have the same comparing the different number of valence electrons. Thus, members of a family families of elements. Include examples of each family in the periodic table share some properties. and describe the common properties of elements in the Group number Number of valence Name of family family. electrons Group 1 1 Alkali metals Group 2 2 Alkaline-earth metals READING CHECK Groups 3–12 varied Transition metals 1. Identify In general, what Group 17 7 Halogens do all elements in the same family have in common? Group 18 8 (except helium, Noble gases which has 2) What Are the Families of Metals? Many elements are classified as metals. Recall that metals can conduct heat and electricity. Most metals can be stretched and shaped into flat sheets or pulled into wires. Families of metals include the alkali metals, the alkaline-earth metals, and the transition metals. THE ALKALI METALS READING CHECK The elements in Group 1 form a family called the 2. Explain Why are alkali alkali metals.