An Array of Layers in Silicon Sulfides: Chain-Like and Ground State
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The Chemistry of Carbene-Stabilized
THE CHEMISTRY OF CARBENE-STABILIZED MAIN GROUP DIATOMIC ALLOTROPES by MARIHAM ABRAHAM (Under the Direction of Gregory H. Robinson) ABSTRACT The syntheses and molecular structures of carbene-stabilized arsenic derivatives of 1 1 i 1 1 AsCl3 (L :AsCl3 (1); L : = :C{N(2,6- Pr2C6H3)CH}2), and As2 (L :As–As:L (2)), are presented herein. The potassium graphite reduction of 1 afforded the carbene-stabilized diarsenic complex, 2. Notably, compound 2 is the first Lewis base stabilized diatomic molecule of the Group 13–15 elements, in the formal oxidation state of zero, in the fourth period or lower of the Periodic Table. Compound 2 contains one As–As σ-bond and two lone pairs of electrons on each arsenic atom. In an effort to study the chemistry of the electron-rich compound 2, it was combined with an electron-deficient Lewis acid, GaCl3. The addition of two equivalents of GaCl3 to 2 resulted in one-electron oxidation of 2 to 1 1 •+ – •+ – give [L :As As:L ] [GaCl4] (6 [GaCl4] ). Conversely, the addition of four equivalents of GaCl3 to 2 resulted in two- electron oxidation of 2 to give 1 1 2+ – 2+ – •+ [L :As=As:L ] [GaCl4 ]2 (6 [GaCl4 ]2). Strikingly, 6 represents the first arsenic radical to be structurally characterized in the solid state. The research project also explored the reactivity of carbene-stabilized disilicon, (L1:Si=Si:L1 (7)), with borane. The reaction of 7 with BH3·THF afforded two unique compounds: one containing a parent silylene (:SiH2) unit (8), and another containing a three-membered silylene ring (9). -
Gas Phase Formation of C-Sic3 Molecules in the Circumstellar Envelope of Carbon Stars
Gas phase formation of c-SiC3 molecules in the circumstellar envelope of carbon stars Tao Yanga,b,1,2, Luke Bertelsc,1, Beni B. Dangib,3, Xiaohu Lid,e, Martin Head-Gordonc,2, and Ralf I. Kaiserb,2 aState Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062, P. R. China; bDepartment of Chemistry, University of Hawai‘iatManoa, Honolulu, HI 96822; cDepartment of Chemistry, University of California, Berkeley, CA 94720; dXinjiang Astronomical Observatory, Chinese Academy of Sciences, Urumqi, Xinjiang 830011, P. R. China; and eNational Astronomical Observatories, Chinese Academy of Sciences, Beijing 100012, P. R. China Contributed by Martin Head-Gordon, May 17, 2019 (sent for review July 20, 2018; reviewed by Piergiorgio Casavecchia and David Clary) Complex organosilicon molecules are ubiquitous in the circumstel- Modern astrochemical models propose that the very first lar envelope of the asymptotic giant branch (AGB) star IRC+10216, silicon–carbon bonds are formed in the inner envelope of the but their formation mechanisms have remained largely elusive until carbon star, which is undergoing mass loss at the rates of several − now. These processes are of fundamental importance in initiating a 10 5 solar masses per year (22, 23). Pulsations from the central chain of chemical reactions leading eventually to the formation of star may initiate shocks, which (photo)fragment the circumstellar — organosilicon molecules among them key precursors to silicon car- materials (24, 25). These nonequilibrium conditions cause tem- — bide grains in the circumstellar shell contributing critically to the peratures of 3,500 K or above (19) and lead to highly reactive galactic carbon and silicon budgets with up to 80% of the ejected metastable fragments such as electronically excited silicon atoms, materials infused into the interstellar medium. -
Rotational Spectroscopy of the Isotopic Species of Silicon Monosulfide, Sisw
PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics Rotational spectroscopy of the isotopic species of silicon monosulfide, SiSw H. S. P. Mu¨ller,*ab M. C. McCarthy,cd L. Bizzocchi,e H. Gupta,cdf S. Esser,g H. Lichau,a M. Caris,a F. Lewen,a J. Hahn,g C. Degli Esposti,e S. Schlemmera and P. Thaddeuscd Received 2nd January 2007, Accepted 23rd January 2007 First published as an Advance Article on the web 20th February 2007 DOI: 10.1039/b618799d Pure rotational transitions of silicon monosulfide (28Si32S) and its rare isotopic species have been observed in their ground as well as vibrationally excited states by employing Fourier transform microwave (FTMW) spectroscopy of a supersonic molecular beam at centimetre wavelengths (13–37 GHz) and by using long-path absorption spectroscopy at millimetre and submillimetre wavelengths (127–925 GHz). The latter measurements include 91 transition frequencies for 28Si32S, 28Si33S, 28Si34S, 29Si32S and 30Si32Sinu = 0, as well as 5 lines for 28Si32Sinu = 1, with rotational quantum numbers J00 r 52. The centimetre-wave measurements include more than 300 newly recorded lines. Together with previous data they result in almost 600 transitions (J00 =0 and 1) from all twelve possible isotopic species, including 29Si36S and 30Si36S, which have fractional abundances of about 7 Â 10À6 and 4.5 Â 10À6, respectively. Rotational transitions were observed from u = 0 for the least abundant isotopic species to as high as u = 51 for the main species. Owing to the high spectral resolution of the FTMW spectrometer, hyperfine structure from the nuclear electric quadrupole moment of 33S was resolved for species containing this isotope, as was much smaller nuclear spin-rotation splitting for isotopic species involving 29Si. -
Standard Thermodynamic Properties of Chemical
STANDARD THERMODYNAMIC PROPERTIES OF CHEMICAL SUBSTANCES ∆ ° –1 ∆ ° –1 ° –1 –1 –1 –1 Molecular fH /kJ mol fG /kJ mol S /J mol K Cp/J mol K formula Name Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Ac Actinium 0.0 406.0 366.0 56.5 188.1 27.2 20.8 Ag Silver 0.0 284.9 246.0 42.6 173.0 25.4 20.8 AgBr Silver(I) bromide -100.4 -96.9 107.1 52.4 AgBrO3 Silver(I) bromate -10.5 71.3 151.9 AgCl Silver(I) chloride -127.0 -109.8 96.3 50.8 AgClO3 Silver(I) chlorate -30.3 64.5 142.0 AgClO4 Silver(I) perchlorate -31.1 AgF Silver(I) fluoride -204.6 AgF2 Silver(II) fluoride -360.0 AgI Silver(I) iodide -61.8 -66.2 115.5 56.8 AgIO3 Silver(I) iodate -171.1 -93.7 149.4 102.9 AgNO3 Silver(I) nitrate -124.4 -33.4 140.9 93.1 Ag2 Disilver 410.0 358.8 257.1 37.0 Ag2CrO4 Silver(I) chromate -731.7 -641.8 217.6 142.3 Ag2O Silver(I) oxide -31.1 -11.2 121.3 65.9 Ag2O2 Silver(II) oxide -24.3 27.6 117.0 88.0 Ag2O3 Silver(III) oxide 33.9 121.4 100.0 Ag2O4S Silver(I) sulfate -715.9 -618.4 200.4 131.4 Ag2S Silver(I) sulfide (argentite) -32.6 -40.7 144.0 76.5 Al Aluminum 0.0 330.0 289.4 28.3 164.6 24.4 21.4 AlB3H12 Aluminum borohydride -16.3 13.0 145.0 147.0 289.1 379.2 194.6 AlBr Aluminum monobromide -4.0 -42.0 239.5 35.6 AlBr3 Aluminum tribromide -527.2 -425.1 180.2 100.6 AlCl Aluminum monochloride -47.7 -74.1 228.1 35.0 AlCl2 Aluminum dichloride -331.0 AlCl3 Aluminum trichloride -704.2 -583.2 -628.8 109.3 91.1 AlF Aluminum monofluoride -258.2 -283.7 215.0 31.9 AlF3 Aluminum trifluoride -1510.4 -1204.6 -1431.1 -1188.2 66.5 277.1 75.1 62.6 AlF4Na Sodium tetrafluoroaluminate -
Iaps Newsletter 2006
IAPS NEWSLETTER 2006 2006 I-APS Newsletter, Volume 28, 2006 1 Contents Letter from the President 3 Letter from the I-APS Newsletter Editor 4 I-APS Officers ` 5 2007 I-APS Awards 6 2006 Porter Awards 6 Howard Zimmerman, the 2006 Porter Medal Laureate 7 Hiroshi Masuhara, the 2006 Porter Medal Laureate 9 2006 I-APS Award Winners 11 Photographs from the I-APS Award Session 15 Research Highlights from the 2006 I-APS Award Winner: Dan Nocera, “Microlasers for High Gain Chemo-/ Bio- Sensing on Small Length Scales” 16 Reports from 2006 Photochemical Meetings 28 In Memoriam Don Arnold 40 George Hammond 41 Upcoming conferences 44 I-APS Membership Form 45 I-APS Newsletter, Volume 28, 2006 2 Letter from the President Cornelia Bohne I-APS President (2006-08) Department of Chemistry University of Victoria PO Box 3065, Victoria, BC Canada V8W 3V6 1-250-7217151 [email protected] http://www.foto.chem.uvic.ca/ August, 2006 Dear Colleagues, I became president of the society a few days after the 17th I-APS Winter Conference held in Salvador, Brazil in June. The meeting was a great success with more than 150 participants, which included about 60 students. The informal atmosphere, leading to vibrant scientific discussions, showed how well integrated the South and North American photochemical communities are. The participation of so many young photochemists bodes well for the future of the photosciences and of the society. During the meeting the society awards were presented to Dan Nocera (I-APS award), Mohammad A. Omary (Young Investigator Award), Ryan C. -
ARTICLE Designing Isoelectronic Counterparts to Layered Group V Semiconductors Zhen Zhu, Jie Guan, Dan Liu, and David Toma´Nek*
ARTICLE Designing Isoelectronic Counterparts to Layered Group V Semiconductors Zhen Zhu, Jie Guan, Dan Liu, and David Toma´nek* Physics and Astronomy Department, Michigan State University, East Lansing, Michigan 48824, United States ABSTRACT In analogy to IIIÀV compounds, which have significantly broadened the scope of group IV semiconductors, we propose a class of IVÀVI compounds as isoelectronic counterparts to layered group V semiconductors. Using ab initio density functional theory, we study yet unrealized structural phases of silicon monosulfide (SiS). We find the black-phosphorus-like R-SiS to be almost equally stable as the blue-phosphorus-like β-SiS. Both R-SiS and β- SiS monolayers display a significant, indirect band gap that depends sensitively on the in-layer strain. Unlike 2D semiconductors of group V elements with the corresponding nonplanar structure, different SiS allotropes show a strong polarization either within or normal to the layers. We find that SiS may form both lateral and vertical heterostructures with phosphorene at a very small energy penalty, offering an unprecedented tunability in structural and electronic properties of SiS-P compounds. KEYWORDS: silicon sulfide . isoelectronic . phosphorene . ab initio . electronic band structure wo-dimensional semiconductors of monosulfide (SiS). We use ab initio density Tgroup V elements, including phos- functional theory (DFT) to identify stable phorene and arsenene, have been allotropes and determine their equilibrium rapidly attracting interest due to their sig- geometry and electronic structure. We have nificant fundamental band gap, large den- identified two nearly equally stable allo- sity of states near the Fermi level, and high tropes, namely, the black-phosphorus-like and anisotropic carrier mobility.1À4 Combi- R-SiS and the blue-phosphorus-like β-SiS, nation of these properties places these and show their structure in Figure 1a and d. -
Inorganic Seminar Abstracts
C 1 « « « • .... * . i - : \ ! -M. • ~ . • ' •» »» IB .< L I B RA FLY OF THE. UN IVERSITY Of 1LLI NOIS 546 1^52-53 Return this book on or before the Latest Date stamped below. University of Illinois Library «r L161— H41 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/inorganicsemi195253univ INORGANIC SEMINARS 1952 - 1953 TABLE OF CONTENTS 1952 - 1953 Page COMPOUNDS CONTAINING THE SILICON-SULFUR LINKAGE 1 Stanley Kirschner ANALYTICAL PROCEDURES USING ACETIC ACID AS A SOLVENT 5 Donald H . Wilkins THE SOLVENT PHOSPHORYL CHLORIDE, POCl 3 12 S.J. Gill METHODS FOR PREPARATION OF PURE SILICON 17 Alex Beresniewicz IMIDODISULFINAMIDE 21 G.R. Johnston FORCE CONSTANTS IN POLYATOMIC MOLECILES 28 Donn D. Darsow METATHESIS IN LIQUID ARSENIC TRICHLORIDE 32 Harold H. Matsuguma THE RHENI DE OXIDATION STATE 40 Robert L. Rebertus HALOGEN CATIONS 45 L.H. Diamond REACTIONS OF THE NITROSYL ION 50 M.K. Snyder THE OCCURRENCE OF MAXIMUM OXIDATION STATES AMONG THE FLUOROCOMPLEXES OF THE FIRST TRANSITION SERIES 56 D.H. Busch POLY- and METAPHOSPHATES 62 V.D. Aftandilian PRODUCTION OF SILICON CHLORIDES BY ELECTRICAL DISCHARGE AND HIGH TEMPERATURE TECHNIQUES 67 VI. £, Cooley FLUORINE CONTAINING OXYHALIDES OF SULFUR 72 E.H. Grahn PREPARATION AND PROPERTIES OF URANYL CARBONATES 76 Richard *• Rowe THE NATURE OF IODINE SOLUTIONS 80 Ervin c olton SOME REACTIONS OF OZONE 84 Barbara H. Weil ' HYDRAZINE BY ELECTROLYSIS IN LIQUID AMMONIA 89 Robert N. Hammer NAPHTHAZARIN COMPLEXES OF THORIUM AND RARE EARTH METAL IONS 93 Melvin Tecotzky THESIS REPORT 97 Perry Kippur ION-PAIR FORMATION IN ACETIC ACID 101 M.M. -
United States Patent (19) 11 Patent Number: 5,843,391 Yamamoto Et Al
USOO584,3391A United States Patent (19) 11 Patent Number: 5,843,391 Yamamoto et al. (45) Date of Patent: Dec. 1, 1998 54 METHOD OF MANUFACTURING SILICON Mellor, “A Comprehensive Treatise on Inorganic and Theo SULFIDE retical Chemistry” vol., VI, QD31 M4, 1947 (no month), pp. 985-990. 75 Inventors: Kazutomi Yamamoto; Nobuhiko Ikeda, both of Hino, Japan European Search Report dated Jun. 23, 1997 for European 73 Assignee: Furukawa Co., Ltd., Tokyo, Japan Applin. No. EP97105989. Chemiker Zeitung, vol. 107, No. 10; 1983 Heidelberg DE, 21 Appl. No.: 839,677 pp. 289-290, R.G. Sobott et al. (no month). 22 Filed: Apr. 15, 1997 “Gmelins Handbuch De Anorganischer Chemie 8" Com 30 Foreign Application Priority Data pletely reworked edition Silicium Part B System-No. 15” 1959 Verlay Chemie, GmbH, p. 747, line 5-line 8. (no Apr. 16, 1996 JP Japan .................................... 8-094396 month). 51) Int. Cl. ............................ C01B33/00; CO1B 17/00 52 U.S. Cl. .......................... 423/344; 423/324; 423/565; 423/DIG. 12 Primary Examiner Ngoc-Yen Nguyen 58 Field of Search ..................................... 423/565,344, Attorney, Agent, or Firm Young & Basile, P.C. 423/324, DIG. 12 57 ABSTRACT 56) References Cited Silicon sulfide is manufactured from the fine powder of U.S. PATENT DOCUMENTS Silicon having a particle size in the range of 60 to 100u, covered thoroughly with Sulfur at lower temperature leSS 2,589,653 3/1952 Alvarez-Tostado et al. ........... 423/344 2,766,103 10/1956 Nielsen et al. .......................... 423/344 than 700 C. in vacuum. In order to produce the silicon 3,321,326 5/1967 Young ............. -
Main Group Multiple Bonds for Bond Activations and Catalysis Catherineweetman*[A]
Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002939 & Main GroupElements |ReviewsShowcase| Main Group Multiple Bonds for Bond Activations and Catalysis CatherineWeetman*[a] Chem. Eur.J.2021, 27,1941 –1954 1941 2020 The Authors. Published by Wiley-VCH GmbH Minireview Chemistry—A European Journal doi.org/10.1002/chem.202002939 Abstract: Since the discovery that the so-called “double- thermore, whilst their ability to act as transition metal bond” rule couldbebroken, the field of molecular main mimics has been explored, their catalytic behaviour is some- group multiple bonds has expanded rapidly.With the major- what limited. This Minireview aims to highlight the potential ity of homodiatomic double and triple bonds realised within of these complexes towards catalytic application and their the p-block, along with many heterodiatomic combinations, role as synthons in furtherfunctionalisations making them a this Minireview examines the reactivity of these compounds versatile tool for the modernsynthetic chemist. with aparticular emphasis on small molecule activation. Fur- Introduction On descending the group the stabilityofthe lower oxidation state increases and thus its desire to partake in bond forma- Molecular main group multiple bond chemistry has rapidly de- tion decreases.For example in group 14, SnII is more stable velopedsince the isolation of the first silicon-silicon double than SnIV,whilst for the lightest congener CIV is more stable bond. West’sdisilene[1] broke the so called “double-bond” rule, than CII.This can also influence the complex formation in both in which it was thought that p-blockelements with aprincipal the solutionand solid state as highlighted by Lappert’s quantum number greater than two (i.e. -
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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
Bonding and Structure of Disilenes and Related Unsaturated Group-14 Element Compounds
No. 5] Proc. Jpn. Acad., Ser. B 88 (2012) 167 Review Bonding and structure of disilenes and related unsaturated group-14 element compounds † By Mitsuo KIRA*1, (Communicated by Hitosi NOZAKI, M.J.A.) Abstract: Structure and properties of silicon-silicon doubly bonded compounds (disilenes) are shown to be remarkably different from those of alkenes. X-Ray structural analysis of a series of acyclic tetrakis(trialkylsilyl)disilenes has shown that the geometry of these disilenes is quite flexible, and planar, twist or trans-bent depending on the bulkiness and shape of the trialkylsilyl substituents. Thermal and photochemical interconversion between a cyclotetrasilene and the corresponding bicyclo[1.1.0]tetrasilane occurs via either 1,2-silyl migration or a concerted electrocyclic reaction depending on the ring substituents without intermediacy of the corresponding tetrasila-1,3-diene. Theoretical and spectroscopic studies of a stable spiropentasiladiene have revealed a unique feature of the spiroconjugation in this system. Starting with a stable dialkylsilylene, a number of elaborated disilenes including trisilaallene and its germanium congeners are synthesized. Unlike carbon allenes, the trisilaallene has remarkably bent and fluxional geometry, suggesting the importance of the :-<* orbital mixing. 14-Electron three-coordinate disilene- palladium complexes are found to have much stronger :-complex character than related 16-electron tetracoordinate complexes. Keywords: silicon, germanium, double bond, synthesis, structure, theoretical calculations -
Nitrogen Versus Phosphorus
The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Electronegativity for carbon: 2.5 Electronegativity for hydrogen: 2.2 Inorganic Chemistry 5.03 The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Electronegativity for carbon: 2.5 Electronegativity for hydrogen: 2.2 Inorganic Chemistry 5.03 The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Electronegativity for carbon: 2.5 Electronegativity for hydrogen: 2.2 Inorganic Chemistry 5.03 The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Quartet ground state, spin multiplicity given by 3 2S + 1 = 2( 2 ) + 1 = 4 3 1 1 3 Four possible values for the spin: + 2 , + 2 , − 2 , − 2 Inorganic Chemistry 5.03 The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Quartet ground state, spin multiplicity given by 3 2S + 1 = 2( 2 ) + 1 = 4 3 1 1 3 Four possible values for the spin: + 2 , + 2 , − 2 , − 2 Inorganic Chemistry 5.03 The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Quartet ground state, spin multiplicity given by 3 2S + 1 = 2( 2 ) + 1 = 4 3 1 1 3 Four possible values for the spin: + 2 , + 2 , − 2 , − 2 Inorganic Chemistry 5.03 Single versus Triple Bonds Atomic energy levels, valence orbital ionization energies (VOIE) ◦ ∆Hf for P2 is +144 kJ/mol ◦ ∆Hf for P≡N is +104 kJ/mol Inorganic Chemistry 5.03 Single versus Triple Bonds Atomic energy levels, valence orbital ionization energies (VOIE) ◦ ∆Hf for P2 is +144 kJ/mol ◦ ∆Hf for P≡N