Bonding and Structure of Disilenes and Related Unsaturated Group-14 Element Compounds
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Contemporary Organosilicon Chemistry
Contemporary organosilicon chemistry Edited by Steve Marsden Generated on 05 October 2021, 02:13 Imprint Beilstein Journal of Organic Chemistry www.bjoc.org ISSN 1860-5397 Email: [email protected] The Beilstein Journal of Organic Chemistry is published by the Beilstein-Institut zur Förderung der Chemischen Wissenschaften. This thematic issue, published in the Beilstein Beilstein-Institut zur Förderung der Journal of Organic Chemistry, is copyright the Chemischen Wissenschaften Beilstein-Institut zur Förderung der Chemischen Trakehner Straße 7–9 Wissenschaften. The copyright of the individual 60487 Frankfurt am Main articles in this document is the property of their Germany respective authors, subject to a Creative www.beilstein-institut.de Commons Attribution (CC-BY) license. Contemporary organosilicon chemistry Steve Marsden Editorial Open Access Address: Beilstein Journal of Organic Chemistry 2007, 3, No. 4. School of Chemistry, University of Leeds, Leeds LS2 9JT, UK doi:10.1186/1860-5397-3-4 Email: Received: 06 February 2007 Steve Marsden - [email protected] Accepted: 08 February 2007 Published: 08 February 2007 © 2007 Marsden; licensee Beilstein-Institut License and terms: see end of document. Abstract Editorial for the Thematic Series on Contemporary Organosilicon Chemistry. The field of organosilicon chemistry has a rich and varied the 1990s, and equivalent to the number appearing in the much history, and has long since made the progression from chemical longer established field of organoboron chemistry -
Aldrichimica Acta
VOLUME 51, NO. 1 | 2018 ALDRICHIMICA ACTA The Spectacular Resurgence of Electrochemical Redox Reactions in Organic Synthesis Carbon–Carbon π Bonds as Conjunctive Reagents in Cross-Coupling The life science business of Merck KGaA, Darmstadt, Germany operates as MilliporeSigma in the U.S. and Canada. MakInG sTrIDes In Genome EDITInG: THe DIGITaL, CHemIcaL, anD BIoLogIcaL Dear Fellow Researchers: You may not know that MilliporeSigma can make DNA from scratch, using 100% synthetic chemical methods—no living cells and no fermentation necessary. Our DNA synthesis facilities in The Woodlands (Texas) and Haverhill (U.K.) receive thousands of DNA orders daily from scientists all over the world. A small piece of DNA, one hundred bases long, gives scientists 4100 possibilities using only the fundamental letters of our genetic code (A,C,G,T). Included within these options is the opportunity for a researcher to open a common text editor on his or her PC and design a 100-base piece of DNA. This piece of DNA could help study diseases ranging from sickle cell anemia and blindness to cystic fibrosis by using CRISPR. To get started, scientists cut this 100-base DNA text from the text editor and paste it into MilliporeSigma’s online ordering system. The corresponding DNA piece that likely has never existed before is then delivered to them in 24–48 hours. Once received, this piece of DNA is mixed with CRISPR and living cells, and, with a “blast” of electricity, these synthetic chemical pieces activate the cell to edit the genome. Learn more about our CRISPR gene editing portfolio at SigmaAldrich.com/CRISPR Sincerely yours, Udit Batra, Ph.D. -
Nigam Prasad Rath Research Professor
Nigam Prasad Rath Research Professor Department of Chemistry and Biochemistry University of Missouri - St. Louis One University Boulevard St. Louis, MO 63121. E-mail: [email protected] Phone: 314-516-5333 FAX: 314-516-5342 Education : B. Sc.(Honors) : 1st Class Honors in Chemistry with Distinction, Berhampur University, Berhampur, India, 1977. M. Sc. (Chemistry): 1st Class, Berhampur University, Berhampur, India, 1979. Ph. D. (Chemistry): Oklahoma State University, Stillwater, OK, USA, 1985. Professional Experience: Research Professor , Department of Chemistry and Biochemistry, University of Missouri, St. Louis, MO, 2004 to present. Research Associate Professor , Department of Chemistry, University of Missouri, St. Louis, MO, 1997 to 2004. Research Assistant Professor , Department of Chemistry, University of Missouri, St. Louis, MO, 1989 to 1996. Assistant Faculty Fellow , Department of Chemistry, University of Notre Dame, Notre Dame, IN 1987 to 1989. Post Doctoral Research Associate , Department of Chemistry, University of Notre Dame, Notre Dame, IN 1986-87. Graduate Assistant , Department of Chemistry, Oklahoma State University, Stillwater, OK 1982 to 1985. Junior Research Fellow (CSIR) , Department of Chemistry, Indian Institute of Technology, Kharagpur, India, 1981-82. Junior Research Fellow , Department of Chemistry, Indian Institute of Technology, Kanpur, India, 1979 to 1981. 2 Professional Positions: Visiting Scientist, Monsanto Corporate Research, Chesterfield, MO, 1992 to 1994. Scientific Consultant, Regional Research Laboratory, Trivandrum, India, 1992 to present. Assistant Professor, Evening College, University of Missouri, St. Louis, 1992 to 2000. Research Mentor, Engelmann Mathematics and Science Institute, University of Missouri, St. Louis, 1990 to 1998. Research Mentor, NSF STARS Program, University of Missouri, St. Louis, 1999 to present. Honors and Awards: National Merit Scholarship, India, 1977-79. -
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). -
Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millennium: a Review
Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millennium: A Review Edgars Abele Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006, Latvia E-mail: [email protected] ABSTRACT Recent advances in the fluoride ion mediated reactions of Si-Η, Si-C, Si-O, Si-N, Si-P bonds containing silanes are described. Application of silicon bonds activation by fluoride ion in the syntheses of different types of organic compounds is discussed. A new mechanism, based on quantum chemical calculations, is presented. The literature data published from January 2001 to December 2004 are included in this review. CONTENTS Page 1. INTRODUCTION 45 2. HYDROSILANES 46 3. Si-C BOND 49 3.1. Vinyl and Allyl Silanes 49 3.2. Aryl Silanes 52 3.3. Subsituted Alkylsilanes 54 3.4. Fluoroalkyl Silanes 56 3.5. Other Silanes Containing Si-C Bond 58 4. Si-N BOND 58 5. Si-O BOND 60 6. Si-P BOND 66 7. CONCLUSIONS 66 8. REFERENCES 67 1. INTRODUCTION Reactions of organosilicon compounds catalyzed by nucleophiles have been under extensive study for more than twenty-five years. In this field two excellent reviews were published 11,21. Recently a monograph dedicated to hypervalent organosilicon compounds was also published /3/. There are also two reviews on 45 Vol. 28, No. 2, 2005 Activation of Silicon Bonds by Fluoride Ion in the Organic Synthesis in the New Millenium: A Review fluoride mediated reactions of fluorinated silanes /4/. Two recent reviews are dedicated to fluoride ion activation of silicon bonds in the presence of transition metal catalysts 151. -
(12) United States Patent (10) Patent No.: US 9,072,293 B2 Yo0 Et Al
US009072293B2 (12) United States Patent (10) Patent No.: US 9,072,293 B2 Yo0 et al. (45) Date of Patent: Jul. 7, 2015 (54) CYCLOPROPENES AND METHOD FOR 6,452,060 B2 9, 2002 Jacobson APPLYING CYCLOPROPENESTO 6,548.448 B2 4/2003 Kostansek 6,762,153 B2 7/2004 Kostansek et al. AGRICULTURAL PRODUCTS OR CROPS 6,953,540 B2 10/2005 Chong et al. 2001/OO 19995 A1 9, 2001 Sisler (75) Inventors: Sang-Ku Yoo, Gyeonggi-do (KR); Jin 2004/00775O2 A1* 4/2004 Jacobson et al. .............. 504,313 Wook Chung, Seoul (KR) 2004/O192554 A1 9/2004 Kashimura et al. 2005/0065033 A1 3/2005 Jacobson et al. .............. 504,343 (73) Assignee: Erum Biotechnologies Inc., 2008/0286426 A1* 11/2008 Yoo ............................... 426,321 Gyeonggi-Do (KR) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this JP 10-94741 4f1998 patent is extended or adjusted under 35 KR 10-2003-0O86982 11, 2003 U.S.C. 154(b) by 0 days. KR 102003OO86982. A * 11, 2003 KR 10-2007-0053113 5/2007 KR 1020070053113 5/2007 (21) Appl. No.: 13/581,797 KR 1020070053113 A * 5, 2007 (22) PCT Filed: Apr. 15, 2011 WO WO O2/068367 9, 2002 OTHER PUBLICATIONS (86). PCT No.: IPRP for related PCT/KR2011/002692 issued on Oct. 23, 2012 and S371 (c)(1), its English translation. (2), (4) Date: Aug. 29, 2012 ISR for related PCT/KR2011/002692 mailed on Jan. 2, 2012 and its English translation. (87) PCT Pub. No.: WO2011/132888 Fumie Sato, et al. “Generation of a Silylethylene-Titanium Alkoxide Complex. -
The Lowest-Energy Isomer of C2si2h4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations
Air Force Institute of Technology AFIT Scholar Faculty Publications 4-11-2019 The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations Jesse J. Lutz ORISE Fellow Larry W. Burggraf Air Force Institute of Technology Follow this and additional works at: https://scholar.afit.edu/facpub Part of the Inorganic Chemistry Commons Recommended Citation Lutz, J. J., & Burggraf, L. W. (2019). The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations. Inorganics, 7(4), 51. https://doi.org/10.3390/inorganics7040051 This Article is brought to you for free and open access by AFIT Scholar. It has been accepted for inclusion in Faculty Publications by an authorized administrator of AFIT Scholar. For more information, please contact [email protected]. inorganics Article The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations Jesse J. Lutz 1,* and Larry W. Burggraf 2 1 ORISE fellow residing at Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson Air Force Base, Dayton, OH 45433-7765, USA 2 Department of Engineering Physics, Air Force Institute of Technology, Wright-Patterson Air Force Base, Dayton, OH 45433-7765, USA; Larry.Burggraf@afit.edu * Correspondence: jesse.lutz.ctr@afit.edu Received: 28 February 2019; Accepted: 3 April 2019; Published: 11 April 2019 Abstract: The lowest-energy isomer of C2Si2H4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). -
Stable Silenolates and Brook-Type Silenes with Exocyclic Structures
Communication pubs.acs.org/Organometallics Terms of Use CC-BY Stable Silenolates and Brook-Type Silenes with Exocyclic Structures † † † † † ‡ Michael Haas, Roland Fischer, Michaela Flock, Stefan Mueller, Martin Rausch, Robert Saf, † † Ana Torvisco, and Harald Stueger*, † ‡ Institute of Inorganic Chemistry and Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austria *S Supporting Information ABSTRACT: The first silenolates with exocyclic structures − + [(Me3Si)2Si(Si2Me4)2SiC(R)O] K (2a: R = 1-adamantyl; 2b: mesityl; 2c: o-tolyl) were synthesized by the reaction of the corresponding acylcyclohexasilanes 1a−c with KOtBu. NMR spectroscopy and single-crystal X-ray diffraction analysis suggest that the aryl-substituted silenolates 2b,c exhibit increased character of functionalized silenes as compared to the alkyl-substituted derivative 2a due to the different coordination of the K+ counterion to the SiC(R)O moiety. 2b,c, thus, reacted with ClSiiPr3 to give the exocyclic silenes (Me3Si)2Si(Si2Me4)2Si C(OSiiPr3)R (3b:R = Mes; 3c: o-Tol), while 2a afforded the Si-silylated acylcyclohex- asilane 1d. The thermally remarkably stable compound 3b, which is the first isolated silene with the sp2 silicon atom incorporated into a cyclopolysilane framework, could be fully characterized structurally and spectroscopically. here is no doubt about the central role of alkenes and Now we would like to report the synthesis, spectroscopic − + fi T metal enolates [(R2CC(R)O] M in organic chemistry, characterization, and molecular structures of the rst cyclic which has led to a thorough understanding of chemical and silenolates (2a−c) and the selective conversion of 2b to the physical properties and numerous applications of such silene 3b, which is the first example of an isolated stable compounds. -
Thermal Rearrangements of Reactive Intermediates in Organosilicon Chemistry Stephanie Ann Burns Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1982 Thermal rearrangements of reactive intermediates in organosilicon chemistry Stephanie Ann Burns Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Burns, Stephanie Ann, "Thermal rearrangements of reactive intermediates in organosilicon chemistry " (1982). Retrospective Theses and Dissertations. 7494. https://lib.dr.iastate.edu/rtd/7494 This Dissertation 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]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. -
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. -
Utilization of the Silicon-Silicon Bond in the Generation of Species Unsaturated at Silicon William Dean Wulff Iowa State University
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1979 Utilization of the silicon-silicon bond in the generation of species unsaturated at silicon William Dean Wulff Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Wulff, William Dean, "Utilization of the silicon-silicon bond in the generation of species unsaturated at silicon " (1979). Retrospective Theses and Dissertations. 6677. https://lib.dr.iastate.edu/rtd/6677 This Dissertation 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]. INFORMATION TO USERS This was produced from a copy of a document sent to us for microfîlming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. -
Organosilicon Compounds for Organic Synthesis
Organosilicon Compounds For Organic Synthesis Introduction Recently, the use of organosilicon compounds in organic chemistry has become an increasingly important field. As such, Shin-Etsu Chemical has been a key supplier for many silylating agents currently in use while also searching for and developing new and useful organosilicon compounds. This booklet introduces several newly developed silylating agents and organosilicon compounds, including references for their application. SILYLATING AGENTS General Definition Silylating agents are reagents that are used to replace the active hydrogen of a chemical species with a silyl group (-Si RR'R"). For example,functional groups such as -OH, -COOH, -NH2, -CONH2, and -SH are converted to -OSiRR'R", -COOSiRR'R", -NHSiRR'R", CONHSiRR'R", and -SSiRR'R",respectively. Purpose In general, the replacement of active hydrogens significantly decreases the reactivity of a functional group and dramatically reduces polar interactions such as hydrogen bonding. These replacements can be carried out for many specific reasons, but typically fall under one or more of the following objectives: (1) Protecting a reactive functional group during one or more chemical reactions (2) Improving the selectivity of a chemical reaction (3) Improving stability during distillation (4) Improving solubility in polar and/or non-polar solvents (5) Increasing volatility by reducing or eliminating hydrogen-bonding How To Select? The most common silylating agents used on an industrial scale are listed in Table I. Reactivity, type of by-product, price, and availability are often important factors that must be considered when the synthetic process is developed. Another important factor to be considered, the stability of the resultant silylated functional group, is largely determined by the combined steric bulk of the alkyl groups attached to silicon (R, R', and R").