DOCSLIB.ORG

Theoretical Study of the Bis-Silylation Reaction of Ethylene Catalyzed by Titanium Dichloride Yuri Alexeev Iowa State University

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Theoretical Study of the Bis-Silylation Reaction of Ethylene Catalyzed by Titanium Dichloride Yuri Alexeev Iowa State University Chemistry Publications Chemistry 8-2003 Theoretical Study of the Bis-Silylation Reaction of Ethylene Catalyzed by Titanium Dichloride Yuri Alexeev Iowa State University Mark S. Gordon Iowa State University, [email protected] Follow this and additional works at: http://lib.dr.iastate.edu/chem_pubs Part of the Chemistry Commons The ompc lete bibliographic information for this item can be found at http://lib.dr.iastate.edu/ chem_pubs/419. For information on how to cite this item, please visit http://lib.dr.iastate.edu/ howtocite.html. This Article is brought to you for free and open access by the Chemistry at Iowa State University Digital Repository. It has been accepted for inclusion in Chemistry Publications by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Theoretical Study of the Bis-Silylation Reaction of Ethylene Catalyzed by Titanium Dichloride Abstract Titanium dichloride was investigated as a potential catalyst for the bis-silylation reaction of ethylene with hexachlorodisilane. Ab initio electronic structure calculations at the restricted Hartree−Fock (RHF), density functional (DFT), second-order perturbation (MP2), and couple cluster (CCSD) levels of theory were used to find optimized structures, saddle points, and minimum-energy paths that connect them. The er action was found to have a net zero barrier at the DFT, MP2, and CCSD levels of theory. Dynamic correlation is found to be important for this reaction. Disciplines Chemistry Comments Reprinted (adapted) with permission from Organometallics 22 (2003): 4111, doi:10.1021/om0303350. Copyright 2014 American Chemical Society. This article is available at Iowa State University Digital Repository: http://lib.dr.iastate.edu/chem_pubs/419 Organometallics 2003, 22, 4111-4117 4111 Theoretical Study of the Bis-Silylation Reaction of Ethylene Catalyzed by Titanium Dichloride Yuri Alexeev and Mark S. Gordon* Department of Chemistry, Iowa State University, Ames, Iowa 50011 Received May 7, 2003 Titanium dichloride was investigated as a potential catalyst for the bis-silylation reaction of ethylene with hexachlorodisilane. Ab initio electronic structure calculations at the restricted Hartree-Fock (RHF), density functional (DFT), second-order perturbation (MP2), and couple cluster (CCSD) levels of theory were used to find optimized structures, saddle points, and minimum-energy paths that connect them. The reaction was found to have a net zero barrier at the DFT, MP2, and CCSD levels of theory. Dynamic correlation is found to be important for this reaction. Introduction the first successful double silylation of 1,3-butadienes using Ni phosphine complexes as catalysts.5 Later The bis-silylation reaction1 is an important process Okinoshima,6 Watanabe,7-9 and others discovered that for producing bis(silyl) compounds and new C-Si bonds, Rh, Ni, Pt, and Pd phosphine complexes can be used to which can serve as monomers for silicon-containing add substituted disilanes across various unsaturated polymers and silicon carbides. Many of these organo- acetylene and ethylene derivatives. It was found that silicon materials have desirable chemical and physical complexes such as M(PPh ) and MCl (PPh ) , where M properties, such as thermal stability and the ability to 3 4 2 3 2 is Pt or Pd, are the most efficient catalysts. Recently store and transfer optical and electrical information.2,3 Bottoni et al.10 used density functional theory (DFT) However, there is a lack of quantum-chemical calcula- with the B3LYP functional11 to study the bis-silylation tions for the study of the effect of catalysis on the bis- reaction of acetylene with disilane, H Si-SiH ,inthe silylation reaction. Such calculations can potentially 3 3 presence of Pd(PH ) . Pd(PH ) was used to emulate Pd- lead to the development of new catalysts. In the bis- 3 2 3 2 (PPh ) , PdCl (PEt ) , and other catalysts often used in silylation reaction an Si-Si bond adds across a C-C 3 2 2 3 2 experimental studies. The net reaction barrier was double or triple bond, in the process breaking a CC π predicted to be 18 kcal/mol. bond and forming two new C-Si bonds. One may write A theoretical study of Pt(PH ) -catalyzed bis-silylation a schematic for the bis-silylation reaction with an alkene 3 2 and hydrosilylation (using the Chalk-Harrod and modi- as fied Chalk-Harrod mechanisms) of alkenes was re- cently performed by Sakaki et al.12,13 These authors used second-order perturbation theory (MP2),14 fourth- order perturbation theory (MP4SDQ),15 and doubles coupled cluster theory (CCD)16 to study the reactions. Experimental and theoretical studies of this reaction The net reaction barrier is predicted to be 19 kcal/mol in the absence of a catalyst suggest that the reaction in the bis-silylation reaction and 5 kcal/mol in the has a high activation barrier. For example, the predicted Chalk-Harrod mechanism of the hydrosilylation reac- barrier height for the addition of disilane to ethylene tion. Thus, the two theoretical studies agree that, even to form 1,2-disilylethane is predicted to be approxi- in the presence of a catalyst, the energy barrier is still mately 50 kcal/mol, using second-order perturbation nontrivial. theory.4 Indeed, this high barrier seems to be insensitive (5) Okinoshima, H.; Yamamoto, K.; Kumada, M. J. Am. Chem. Soc. to the level of theory employed. This suggests, as is well- 1972, 94, 9263. known to experimentalists, that a catalyst is required (6) Okinoshima, H.; Yamamoto, K.; Kumada, M. J. Organomet. to make this reaction practical, certainly in any indus- Chem. 1975, 86, C27. (7) Watanabe, H.; Kobayashi, M.; Saito, M.; Nagai, Y. J. Organomet. trial sense. Chem. 1981, 149, 216. A number of bis-silylation catalysts have been em- (8) Watanabe, H.; Saito, M.; Sutou, N.; Kishimoto, K.; Inose, J.; Nagai, Y. J. Organomet. Chem. 1982, 225, 343. ployed since 1972, when Okinoshima et al. carried out (9) Watanabe, H.; Kitahara, T.; Motegi, T.; Nagai, Y. J. Organomet. Chem. 1977, 215, 139. * Corresponding author. (10) Bottoni, A.; Higueruelo, A. P.; Miscione, G. P. J. Am. Chem. (1) Jones, R. G.; Ando, W.; Chojnowski, J. Silicon-Containing Soc. 2002, 124, 5506. Polymers: The Science and Technology of Their Synthesis and Ap- (11) Koch, W.; Holthausen, M. C. A Chemist’s Guide to Density plications; Kluwer Academic: Dordrecht, The Netherlands, 2000. Functional Theory; Wiley: Weinheim, Germany, 2000. (2) (a) Lee, H. H. Fundamentals of Microelectronic Processing; (12) Sakaki, S.; Ogawa, M.; Musashi, Y. J. Organomet. Chem. 1997, McGraw-Hill: New York, 1990. (b) Mort, J.; Jansen, F. Plasma 535, 25. Deposited Thin Films; CRC Press: Boca Raton, FL, 1986. (c) Sueta, (13) Sakaki, S.; Mizoe, N.; Sugimoto, M.; Musashi, Y. Coord. Chem. T.; Okoshi, T. Ultrafast and Ultra-Parallel Optoelectronics; Wiley: Rev. 1999, 190-192, 933. Tokyo, 1995. (d) Prasad, P. N.; Ulrich, D. R. Nonlinear Optical and (14) Moler, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618. Electroactive Polymers; Plenum Press: New York, 1988. (15) Cramer, C. J. Essentials of Computational Chemistry; Wiley: (3) (a) Bradley, D. C. Chem. Rev. 1989, 89, 1317. (b) Hench, L. L.; New York, 2000. West, J. K. Chem. Rev. 1990, 90, 33. (16) Crawford, T. D.; Schaefer, H. F., III. Rev. Comput. Chem. 1996, (4) Raaii, F.; Gordon, M. S. J. Phys. Chem. A 1998, 102, 4666. 14, 33. 10.1021/om0303350 CCC: $25.00 © 2003 American Chemical Society Publication on Web 08/30/2003 4112 Organometallics, Vol. 22, No. 20, 2003 Alexeev and Gordon It is well-known that complexes of early transition the catalytic activity is similar in the Ziegler-Natta and metals, such as Ti and Zr, exhibit catalytic properties. hydrosilylation reactionssthe initial formation of a very In the Ziegler-Natta polymerization reaction, the com- stable intermediate. monly used catalysts are MCl4-AlR3 and MR2, where The purpose of the present work is to present ab initio MisTiorZr.17 The first step in the currently accepted calculations on possible mechanisms for the catalyzed mechanism is formation of a metal-alkyl-olefin com- bis-silylation reaction. On the basis of the discussion in + plex. The addition of Cl2TiCH3 to C2H4 was studied the previous paragraph, TiCl2 is used as a model recently by Bernardi et al.18 with DFT using the B3LYP catalyst for the bis-silylation reaction of ethylene with functional. The reaction is predicted to require no net hexachlorodisilane. This choice of reactants allows us barrier. A π-complex intermediate that is found to be to study this reaction at reliable levels of theory without lower in energy than the reactants by 38 kcal/mol compromising accuracy, and, as noted above, TiCl2 is apparently drives this catalyzed reaction by providing expected to reliably mimic TiCp2. Since TiCp2 is thought an initially large exothermicity. to be the active industrial catalyst for producing organ- Titanocene- (TiCp2, where Cp ) cyclopentadienyl) and osilicon polymers on the basis of the results of Harrod 20 19 zirconocene-based catalysts (ZrCp2) were recently re- et al. and the recent report by Terao et al., it is ported to be efficient catalysts for double silylation by reasonable to consider TiCl2 as a viable model for the 19 Terao et al. and Harrod et al. In particular, double efficient catalyst TiCp2. silylation of isoprene with chlorotriethylsilane proceeds with 91% yield at 0 °C in the presence of Cp2TiCl2 and Computational Methods BuMgCl in THF solution. The double silylation of p-chlorostyrene by Me PhSiCl in the presence of BuMgCl All calculations performed for this paper were carried out 2 using the GAMESS program,22 and figures were generated and Cp TiCl in THF solution under the same conditions 2 2 using the MacMolPlt program.23 The basis set used in the gives a 72% yield.
Load more

Recommended publications
  • Low Pressure Chemical Vapor Deposition of A-Si:H from Disilane Cole Petersburg Iowa State University
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2007 Low pressure chemical vapor deposition of a-Si:H from disilane Cole Petersburg Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Electrical and Electronics Commons, and the Materials Science and Engineering Commons Recommended Citation Petersburg, Cole, "Low pressure chemical vapor deposition of a-Si:H from disilane" (2007). Retrospective Theses and Dissertations. 14557. https://lib.dr.iastate.edu/rtd/14557 This Thesis is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Low pressure chemical vapor deposition of a-Si:H from disilane by Cole Petersburg A thesis submitted to the graduate faculty in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Major: Electrical Engineering Program of Study Committee: Vikram Dalal, Major Professor Kristen Constant Santosh Pandey Iowa State University Ames, Iowa 2007 Copyright c Cole Petersburg, 2007. All rights reserved. UMI Number: 1443091 UMI Microform 1443091 Copyright 2007 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, MI 48106-1346 ii TABLE OF CONTENTS LIST OF TABLES . iv LIST OF FIGURES .
    [Show full text]
  • Primer on Spontaneous Heating and Pyrophoricity
    NOT MEASUREMENT SENSITIVE DOE‐HDBK‐1081‐2014 Supersedes DOE‐HDBK‐1081‐94 DOE HANDBOOK PRIMER ON SPONTANEOUS HEATING AND PYROPHORICITY U.S. Department of Energy FSC‐6910 Washington, D.C. 20585 DISTRIBUTION STATEMENT: Approved for public release; distribution is unlimited. This document is available on the Department of Energy Technical Standards Program Web page at: http://www.hss.doe.gov/nuclearsafety/ns/techstds/ Key words: Alkali Metals , Aluminum, Arsine, Calcium, Class D Extinguishing Agents, Coal Storage, Combustible Metals, Diborane, Fire, Hafnium, Heating, Hydrazine, Hydrocarbons, Hypergolic, Hypergolic Reaction, Iron, Lithium, Magnesium, Metals, Microbial Heating, NaK, Organic, Oxidizer, Phosphine, Phosphorus, Plutonium, Potassium, Pyrophoric, Pyrophoricity, Pyrophoric Gases, Pyrophoric Reagents, Silane Specific Area, Sodium, Sodium‐Potassium, Specific Surface Area, Spontaneous, Spontaneous Combustion, Steel, Super Oxides, Thorium, Titanium, Uranium, Water Reactive Metals, Zinc, Zirconium FOREWORD The Primer on Spontaneous Heating and Pyrophoricity is approved for use by all DOE Components. It was developed to help Department of Energy (DOE) facility contractors prevent fires caused by spontaneous ignition. Spontaneously ignitable materials include those that ignite because of a slow buildup of heat (spontaneous heating) and those that ignite in air (pyrophoricity). The scientific principles of combustion and how they affect materials known to be spontaneously combustible are explained. The fire hazards of specific spontaneously heating and pyrophoric materials are discussed as well as techniques to prevent their ignition. Suitable fire extinguishing agents are included for most materials as well as safety precautions for storage and handling. The DOE Primers are fundamental handbooks on safety‐related topics of interest in the DOE Complex and are intended as an educational aid for operations and maintenance personnel and others who may have an interest in this topic.
    [Show full text]
  • Silanes As Ligands in Transition Metal Coordination Chemistry
    inorganics Article (2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry Lisa Ehrlich 1, Robert Gericke 1 , Erica Brendler 2 and Jörg Wagler 1,* 1 Institut für Anorganische Chemie, TU Bergakademie Freiberg, D-09596 Freiberg, Germany; [email protected] (L.E.); [email protected] (R.G.) 2 Institut für Analytische Chemie, TU Bergakademie Freiberg, D-09596 Freiberg, Germany; [email protected] * Correspondence: [email protected]; Tel.: +49-3731-39-4343 Received: 29 September 2018; Accepted: 26 October 2018; Published: 31 October 2018 Abstract: Proceeding our initial studies of compounds with formally dative TM!Si bonds (TM = Ni, Pd, Pt), which feature a paddlewheel arrangement of four (N,S) or (N,N) bridging ligands around the TM–Si axis, the current study shows that the (N,O)-bidentate ligand 2-pyridyloxy (pyO) is also capable of bridging systems with TM!Si bonds (shown for TM = Pd, Cu). Reactions of MeSi(pyO)3 with [PdCl2(NCMe)2] and CuCl afforded the compounds MeSi(µ-pyO)4PdCl (1) and MeSi(µ-pyO)3CuCl (2), respectively. In the latter case, some crystals of the Cu(II) compound MeSi(µ-pyO)4CuCl (3) were obtained as a byproduct. Analogous reactions of Si(pyO)4, in the presence of HpyO, with [PdCl2(NCMe)2] and CuCl2, afforded the compounds [(HpyO)Si(µ-pyO)4PdCl]Cl (4), (HpyO)2Si[(µ-pyO)2PdCl2]2 (5), and (HpyO)2Si[(µ-pyO)2CuCl2]2 (6), respectively. Compounds 1–6 and the starting silanes MeSi(pyO)3 and Si(pyO)4 were characterized by single-crystal X-ray diffraction analyses and, with exception of the paramagnetic compounds 3 and 6, with NMR spectroscopy.
    [Show full text]
  • Ereztech LLC SI0687 Safety Data Sheet
    EREZTECH LLC 11555 Medlock Bridge Road, Suite 100, Johns Creek, GA 30097, USA T: +1.888.658.1221 F: 1.678.619.2020 E: [email protected] W: https://ereztech.com Section 1. Identification Product Name: Hexafluorodisilane Product Type: Gas CAS Number: 13830-68-7 Product Number: SI0687 Product Manufacturer: Ereztech LLC 11555 Medlock Bridge Road, Suite 100 Johns Creek, GA 30097 Product Information: (888) 658-1221 In case of an emergency: CHEMTREC: 1-800-424-9300 (USA); +1 703-527-3887 (International); CCN836180 *** Contact manufacturer for all non-emergency calls. Section 2. Hazards Identification Hazards Identification Classification: GASES UNDER PRESSURE – Compressed Gas, H280 SKIN CORROSION/IRRITATION; - Category 1B, H314 SERIOUS EYE DAMAGE/EYE IRRITATION - Category 1, H318 ACUTE TOXICITY, INHALATION; - Category 3, H331 SPECIFIC TARGET ORGAN TOXICITY, SINGLE EXPOSURE; RESPIRATORY TRACT IRRITATION - Category 3, H335 GHS label elements Hazard pictograms: Signal word: DANGER Hazard statements: H280: Contains gas under pressure; may explode if heated. H314: Causes severe skin burns and eye damage. H318: Causes serious eye damage. H331: Toxic if inhaled. H335: May cause respiratory irritation. Ereztech SI0687 Page 1 of 13 Revision: 1.10 Date of Issue: 1/4/20 Hexafluorodisilane Safety Data Sheet Section 2. Hazards Identification Precautionary statements Prevention: P260: Avoid breathing vapors and gases. P264: Wash skin thoroughly after handling. P271: Use only outdoors or in a well-ventilated area. P280: Wear protective gloves/ protective clothing/ eye protection/ face protection. Response: P301 + P330 + P331: IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. P303 + P361 + P353: If on skin (or hair): Take off immediately all contaminated clothing.
    [Show full text]
  • Synthesis of Di- and Trisilanes with Potentially Chelating Substituents
    Journal of Organometallic Chemistry 649 (2002) 25–42 www.elsevier.com/locate/jorganchem Synthesis of di- and trisilanes with potentially chelating substituents Johannes Belzner a,1*, Uwe Dehnert a, Dirk Scha¨r a, Bernhard Rohde a, Peter Mu¨ller b, Isabel Uso´n b a Institut fu¨r Organische Chemie der Georg-August-Uni6ersita¨t Go¨ttingen, Tammannstr. 2, D-37077 Go¨ttingen, Germany b Institut fu¨r Anorganische Chemie der Georg-August-Uni6ersita¨t Go¨ttingen, Tammannstr. 4, D-37077 Go¨ttingen, Germany Received 3 April 2001; received in revised form 29 May 2001; accepted 29 October 2001 Abstract Silylenes 2 or 4, generated by thermolysis of cyclotrisilanes 1 and 3, were inserted into the SiCl or SiH bonds of monosilanes to yield a variety of disilanes, which can be further functionalized subsequently. In a few cases, trisilanes are accessible by the reaction of 1 with disilanes. The reaction of a metalated silane with a chlorosilane is an alternative method for the formation of SiSi bonds, which turned out to be especially useful for the synthesis of bulkily substituted disilanes. Some of the new dichlorodi- and trisilanes themselves serve as thermal precursors of silylenes 2 or 4, the extrusion of which can be catalyzed by 1 or 3 in certain cases. © 2002 Elsevier Science B.V. All rights reserved. Keywords: Silylenes; Oligosilanes; Halosilanes; Siliconsilicon bond formation 1. Introduction crucial intermediate—to the formation of symmetri- cally substituted disilanes [1]. In contrast, geminally Two principal reaction pathways are available for the dihalogenated silanes do not serve as synthetically use- formation of SiSi bonds (Scheme 1).
    [Show full text]
  • Ideal Gas Thermochemistry of Silicon Inorganic Organic and Ion Compounds
    This is the peer reviewed version of the following article: Alexander Burcat, Elke Goos, Ideal gas thermochemical properties of silicon containing inorganic, organic compounds, radicals, and ions, Int J Chem Kinet. 2018;50:633–650, which has been published in final form at http://dx.doi.org/10.1002/kin.21188. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. 1 Ideal Gas Thermochemical Properties of Silicon containing Inorganic, Organic Compounds, Radicals and Ions. Alexander Burcat Faculty of Aerospace Engineering, Technion- Israel Institute of Technology, Haifa 32000, Israel, [email protected] and Elke Goos, Institute of Combustion Technology, Deutsches Zentrum für Luft- und Raumfahrt e.V. (DLR, German Aerospace Center), Pfaffenwaldring 38, 70569 Stuttgart, Germany. [email protected] ABSTRACT The ideal gas thermochemical properties such as standard heat of formation, entropy and heat capacities of 112 inorganic and 35 organic neutral compounds, radicals and ions containing silicon were calculated using molecular properties obtained with the G3B3 (or G3//B3LYP) method. Among them were linear and cyclic silanes, silenes, hydrocarbonsilanes, fluorine and oxygen containing compounds. Many of their molecular and thermodynamic properties were calculated for the first time and 16 of them had no CAS No. Additionally the thermochemical properties were presented in the NASA 7-term polynomial format for the temperature range of 200 K to 6000 K commonly used in chemical kinetic modeling and simulation programs. The polynomials are available in the supplement to this article free of charge. 2 KEYWORDS Thermodynamic data, Thermochemistry, Thermochemical properties, Heat of formation, Entropy, Enthalpy, Heat capacity, NASA format, Quantum chemical calculation, G3B3 composite approach, Silicon hydride, Silanes, Silicon fluoride, Silicon hydrocarbon, Silicon ions, Silicon compounds, Database INTRODUCTION Silicon containing substances are widely used and important for the mankind.
    [Show full text]
  • Toxic and Highly Toxic Gas Handling Procedure
    Environmental Health and Safety Toxic and Highly Toxic Gas Handling Procedure Date of Issuance: 10/2019 Revision Date: 5/27/2021 Revision Number: 1 Prepared by: EHS 1. Scope and Background The Carnegie Mellon University Toxic and Highly Toxic Gas Handling Program specifies minimum requirements for safe storage, use, and handling of toxic and highly toxic gas at Carnegie Mellon University. This program has been approved by the Laboratory Safety Committee. This document: • summarizes the health and safety risks associated with toxic and highly toxic gas use and handling; • identifies exposure control methods to protect employee’s safety and health and the environment; • outlines regulatory and university requirements related to this work; • specifies emergency response procedures for addressing toxic gas issues; and • provides resources for further information. Toxic and highly toxic gases are gases that may cause significant acute health effects at low concentrations. Health effects may include severe skin or eye irritation, pulmonary edema, neurotoxicity or other potentially fatal conditions. The criteria used to establish the materials addressed by this policy are: • A National Fire Protection Association (NFPA) health rating of 3 or 4 • An NFPA health rating of 2 with poor physiological warning properties • Pyrophoric (self-igniting) characteristics, OR • An extremely low occupational exposure limits in the absence of an NFPA health rating. Table 1 identifies common gases that meet the criteria of toxic or highly toxic, though it is
    [Show full text]
  • The Chemical List of Interest
    List of Toxic and Pyrophoric Gases that require preappro val from MSU EHS BEFORE purc hase Chemical MSDS CAS # Health Fire Reactive 1,3-BUTADIENE 1,3-BUTADIENE 106-99-0 2d 4 0 2-METHYL-1,3-BUTADIENE 2-METHYL-1,3-BUTADIENE 78-79-5 1i 4 0 ACETYL FLUORIDE ACETYL FLUORIDE 557-99-3 3 0 0 AMMONIA AMMONIA 7664-41-7 3 1 0 ANTIMONY PENTAFLUORIDE ANTIMONY PENTAFLUORIDE 7783-70-2 4 0 1 ARSENIC PENTAFLUORIDE ARSENIC PENTAFLUORIDE 7784-36-3 3 1 0 ARSENIC TRIFLUORIDE ARSENIC TRIFLUORIDE 7784-35-2 3 0 1 ARSINE ARSINE 7784-42-1 4 4 2 BIS(TRIFLUOROMETHYL)PEROXIDE BIS(TRIFLUOROMETHYL)PEROXIDE 927-84-4 a, j a, j a, j BORON TRIBROMIDE BORON TRIBROMIDE 10294-33-4 4 2 0 BORON TRICHLORIDE BORON TRICHLORIDE 10294-34-5 3 0 1 BORON TRIFLUORIDE BORON TRIFLUORIDE 7637-07-2 4 0 1 BROMINE BROMINE 7726-95-6 3 0 0 BROMINE CHLORIDE BROMINE CHLORIDE 13863-41-7 3 0 1 BROMINE PENTAFLUORIDE BROMINE PENTAFLUORIDE 7789-30-2 3 0 3 BROMINE TRIFLUORIDE BROMINE TRIFLUORIDE 7787-71-5 3 0 3 BROMOETHENE BROMOETHENE 593-60-2 2d 4 1 BROMOMETHANE BROMOMETHANE 74-83-9 3 1 0 CARBON DISULFIDE CARBON DISULFIDE 75-15-0 3 4 0 CARBON MONOXIDE CARBON MONOXIDE 630-08-0 2e 4 0 CARBONYL FLUORIDE CARBONYL FLUORIDE 353-50-4 4 0 1 CARBONYL SULFIDE CARBONYL SULFIDE 463-58-1 3 4 1 CHLORINE CHLORINE 7782-50-5 4 0 0 CHLORINE DIOXIDE CHLORINE DIOXIDE 10049-04-4 3 0 4 CHLORINE MONOXIDE CHLORINE MONOXIDE 12301-79-0 a a a CHLORINE PENTAFLUORIDE CHLORINE PENTAFLUORIDE 13637-63-3 3 0 3 CHLORINE TRIFLUORIDE CHLORINE TRIFLUORIDE 7790-91-2 4 0 3 CHLOROTRIFLUOROETHYLENE CHLOROTRIFLUOROETHYLENE 79-38-9 3 4 3 CARBON
    [Show full text]
  • Mastercommission 9K
    r V f .6 1 .*......'=r t63 - t-1 f 3 - 1( 15. Reasilons of BecRiling Silicon Bteg with Phosphine Silane BBd Disilane 1 h -----=- -- --------- ---=--- ---=- =-=- =-------- -=---- --= -=----=- to (1) Financial support from the United States Atomic EnergyMASTERCommission 9K t is gratefully acknowledged. This is · AEC report No. COO-1713-16. -40 M 1 -0..1 The formation of disilane and silane H331 SiSiH3 the fast-neutro'n +d 31 SiH4 from CD , irradiation of phosphine-silane mixtures has been rationalized by proposing a ia. 0.V' set of product-determing steps involving the intermediate silylene: 31 SiH2 - which is the product of the primary reactions of recoiling silicon atoms.2 31PH + ·n ;631Si + p + 3 H: :':· ' 1, 1- 3 gi ...:»,. : 3·1 •••••••• ) :31 SiH 2 44 U 1 9.: . ..'. X"" f .:31 SiH2 + SiH4 ·H-31.1 SiSiHi v i - 6'' I b . 3 1 SiH · · , · :31 SiH2 + SiH4 4 ,4 31 SiH :31 SiH2 + PH3 4 ; involatile material :3 1 SiH2 ' ' PH3 ., L 0 1 . 9. (2) P.P. Gaspar, S.A. B·ock and W.. C. Eckelman, J. Amer. Chem. Soc., 22, 6914 (1968). ..R' The present report provides support,for the intermediacy of :31 SiH and suggests the occurence of a novel reaction:-.the insertion of :31 SiH into silicon- 2 silicon bonds. *$.An mechanism for the formation gf involving the ·1 . ternative H331SiSiH3 coupling of silyl radicals, '31 SiH3 with nonradioactive 'SiH3 formed from . : A: silane by radiation damage „ had been ·rendered unlikely by the failure of ' scavengers to-affect product yields. 2, '.However; the reaction , :- (NO,.C2H4-).
    [Show full text]
  • An Introduction to Basic Silicone Chemistry By
    [ 01 ft< 58449 > OU_1 [g ^ CD ^ C/) LI ' Call No. - ~L> Accession No. Author fidCJi*lO. Tak CL^v betew. This book should be re/Urned on or before the date last marked An Introduction to the CHEMISTRY of the SILICONES An Introduction to the CHEMISTRY of the SILICONES By EUGENE G. ROCHOW Research Laboratory, General Electric Company NEW YORK: JOHN WILEY & SONS, INC. LONDON: CHAPMAN & HALL, LIMITED COPYRIGHT, 1946 BY EUGENE G. ROCHOW AU Rights Reserved This book or any part thereof must not be reproduced in any form without the written permission of the publisher. SECOND PRINTING, MARCH, 1947 PRINTED IN THE UNITED STATES OF AMERICA To P. G. F. PREFACE The organic compounds of silicon, which have been the subject of many scholarly researches during the past 80 years, at last show promise of emerging from the laboratory and finding a place in industry. An understanding of the behavior of organosilicon materials is necessary to their intelligent use and, inasmuch as the chemistry of these substances ordinarily is not treated in our textbooks, it is possible that a compact yet comprehensive survey of our present knowledge in this field would be of service to chemists, engineers, and industrial designers. This volume has just such a purpose. The first few chapters review the silanes and their derivatives in some detail, in order to provide an understanding of the fundamental chemistry of the nonsilicate com- pounds of silicon. The later chapters emphasize the silicone polymers which have achieved commercial importance and deal with the methods for their preparation, their chemical and physical properties, and their possible usas.
    [Show full text]
  • Supporting Information To: Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections
    Supporting information to: Long-range corrected hybrid density functionals with improved dispersion corrections 1 1 1 1, 2, You-Sheng Lin, Guan-De Li, Shan-Ping Mao, and Jeng-Da Chai ⇤ 1Department of Physics, National Taiwan University, Taipei 10617, Taiwan 2Center for Theoretical Sciences and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan TABLE S1. Vertical IPs of IP131 database (page SI 2). TABLE S2. Vertical EAs of EA115 database (page SI 7). TABLE S3. Fundamental gaps of FG115 database (page SI 11). TABLE S4. Atomic energies from H to Ar (page SI 15). TABLE S5. NHTBH38/04 barrier heights (page SI 16). TABLE S6. HTBH38/04 barrier heights (page SI 17). TABLE S7. Interaction energies for S22 (page SI 18). TABLE S8. Reaction energies (page SI 19). TABLE S9. Binding energies of noncovalent interactions (page SI 19). Reference (page SI 21). ⇤ Author to whom correspondence should be addressed. Electronic mail: [email protected]. SI 2 TABLE S1: -✏N (N) (in eV) by DFT methods in the IP131 database. [1] Molecule Reference !M06-D3 !B97X-D3 M06-2X H (Hydrogen atom) 13.60 11.67 11.37 10.31 He (Helium atom) 24.59 21.24 20.62 20.56 Li (Lithium atom) 5.39 5.25 5.30 4.19 Be (Beryllium atom) 9.32 8.57 8.49 7.26 B (Boron atom) 8.30 7.70 7.51 6.17 C (Carbon atom) 11.26 10.23 9.87 8.84 N (Nitrogen atom) 14.53 12.92 12.46 11.78 O (Oxygen atom) 13.62 12.29 11.83 11.21 F (Fluorine atom) 17.42 15.53 14.96 14.82 Ne (Neon atom) 21.57 19.01 18.39 18.66 Na (Sodium atom) 5.14 5.09 4.92 4.19 Mg (Magnesium atom)
    [Show full text]
  • Supplementary Material To: Long-Range Corrected Hybrid Meta-Generalized-Gradient Approximations with Dispersion Corrections
    Supplementary material to: Long-range corrected hybrid meta-generalized-gradient approximations with dispersion corrections You-Sheng Lin,1 Chen-Wei Tsai,1 Guan-De Li,1 and Jeng-Da Chai1, 2, ∗ 1Department of Physics, National Taiwan University, Taipei 10617, Taiwan 2Center for Theoretical Sciences and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan TABLE S1. Vertical IPs of IP131 database (page S2). TABLE S2. Vertical EAs of EA115 database (page S6). TABLE S3. Fundamental gaps of FG115 database (page S10). TABLE S4. Molecular geometries of IP131, EA115 and FG115 (page S15). TABLE S5. Atomic energies from H to Ar (page S41). TABLE S6. NHTBH38/04 barrier heights (page S42). TABLE S7. HTBH38/04 barrier heights (page S43). TABLE S8. Interaction energies for S22 (page S44). TABLE S9. Reaction energies (page S45). TABLE S10. Binding energies of noncovalent interactions (page S46). Reference (page S47). ∗ Author to whom correspondence should be addressed. Electronic mail: [email protected]. S2 TABLE S1: -N (N) (in eV) of IP131 database. Most ex- perimental reference values are collected from the NIST database, [1] while other publications [2{14] are adopted for the molecules marked. Molecule Reference !M05-D M05-2X !B97X-D H (Hydrogen atom) 13.60 11.10 10.44 11.04 He (Helium atom) 24.59 20.75 20.75 20.18 Li (Lithium atom) 5.39 5.06 4.19 5.22 Be (Beryllium atom) [2] 9.32 8.19 7.29 8.27 B (Boron atom) 8.30 7.21 6.39 7.24 C (Carbon atom) 11.26 9.74 9.11 9.57 N (Nitrogen atom) 14.53 12.46 12.02 12.13
    [Show full text]