Organosilicon Compounds: Experiment (Physico-Chemical Studies) and Applications PDF
Preview Organosilicon Compounds: Experiment (Physico-Chemical Studies) and Applications
Organosilicon Compounds From Theory to Synthesis to Applications, Volume 2 Organosilicon Compounds Experiment (Physico-Chemical Studies) and Applications Edited by Vladimir Ya. Lee University of Tsukuba, Tsukuba, Japan AcademicPressisanimprintofElsevier 125LondonWall,LondonEC2Y5AS,UnitedKingdom 525BStreet,Suite1800,SanDiego,CA92101-4495,UnitedStates 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom Copyrightr2017ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronicormechanical,including photocopying,recording,oranyinformationstorageandretrievalsystem,withoutpermissioninwritingfromthepublisher. Detailsonhowtoseekpermission,furtherinformationaboutthePublisher’spermissionspoliciesandourarrangementswith organizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency,canbefoundatourwebsite: www.elsevier.com/permissions. ThisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythePublisher(otherthanasmaybe notedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperiencebroadenourunderstanding, changesinresearchmethods,professionalpractices,ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluatingandusingany information,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethodstheyshouldbe mindfuloftheirownsafetyandthesafetyofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeanyliabilityforany injuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuseor operationofanymethods,products,instructions,orideascontainedinthematerialherein. BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress ISBN:978-0-12-814213-4 ForInformationonallAcademicPresspublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:JohnFedor AcquisitionEditor:EmilyM.McCloskey EditorialProjectManager:SusanE.Ikeda ProductionProjectManager:MohanapriyanRajendran CoverDesigner:MatthewLimbert TypesetbyMPSLimited,Chennai,India List of Contributors RosaBecerra Institute ofPhysical Chemistry, ‘Rocasolano’,CSIC, Madrid, Spain Anna Chrostowska Universite´ de Pau et des Pays del’Adour, Pau, France ClovisDarrigan Universite´ dePauet des Pays del’Adour,Pau,France MichiyaFujiki NaraInstituteof Science andTechnology (NAIST),Nara, Japan Galina M.Ignat’eva Enikolopov InstituteofSyntheticPolymeric Materials RAS,Moscow, Russia DimitrisE. Katsoulis Dow Corning Corporation, Midland, MI, United States JulianKoe International Christian University,Tokyo, Japan HieronimMaciejewski AdamMickiewicz Universityin Poznan´, Poznan´,Poland Bogdan Marciniec Adam Mickiewicz UniversityinPoznan´, Poznan´, Poland Aziz M.Muzafarov A.N. Nesmeyanov Institute ofOrganoelement Compounds RAS, Moscow, Russia; Enikolopov Institute ofSyntheticPolymeric Materials RAS,Moscow, Russia Benedikt Niepo¨tter University ofGo¨ttingen, Go¨ttingen, Germany PiotrPawluc´ Adam Mickiewicz UniversityinPoznan´, Poznan´, Poland RandallG.Schmidt Dow Corning Corporation, Midland,MI, United States DietmarStalke Universityof Go¨ttingen,Go¨ttingen,Germany Elena A.Tatarinova EnikolopovInstitute ofSyntheticPolymeric Materials RAS, Moscow, Russia FrankUhlig GrazUniversityof Technology,Graz, Austria NataliaV. Vasilenko Enikolopov Institute ofSynthetic Polymeric Materials RAS, Moscow, Russia RobinWalsh University ofReading, Reading, United Kingdom GreggA. Zank DowCorning Corporation, Midland, MI, United States xi About the Editor Vladimir LEE earned his PhD from the N.D. Zelinsky Institute of Organic Chemistry Academy of Sciences in the USSR. Following two postdoctoral stints and a number of years working at universities and research institutes, he currently holds the position of Lecturer at the University of Tsukuba (Tsukuba, Japan). His career in the field of main group, mostly organosilicon, chemistry has spanned a period of over 30 years, with a predominant focus on the study (both experimental and theoretical) of the low-coordinate derivatives of the main group elements: cations, radicals, anions, carbenes, multiply-bonded species, aromatic compounds, clusters, and transition metal complexes. His work is documented in over 120 publications. xiii Preface Organosilicon chemistry deals with those compounds featuring carbon(cid:1)silicon bonds that have been known since Friedel and Crafts landmark report of 1863 on the first organosilicon derivative, tetraethylsilane. By the present day, organosilicon reagents have become omnipresent, used in a wide variety of organic processes. Given the importance of these compounds, it comes as no surprise that organosilicon chemistry is repeatedly reviewed and discussed; and as the field continues to grow, there is a continual need for regular updates on its latest advances. That is the reason why we have attempted in this book to survey, analyze, and summarize the current state of affairs in the field of organosilicon chemistry, focusing on the most recent (published mostly after 2000) milestone advances and covering the literature up to the beginning of 2017. As a reflection of the research and development process, and also in line with its title, Organosilicon Compounds: From Theory to Synthesis to Applications, this book comprises three parts, “Theory,” “Experiment,” and “Applications,” made up of a total of 19 chapters, written by leading experts in their respective fields. Given the great number of chapters and a total of more than 1000 pages, the text has been broken up into 2 volumes: Volume 1, Theory and Experiment (Synthesis), covering computational and synthetic aspects of organosilicon chemistry, and Volume 2, Experiment (Physico-Chemical Studies) and Applications, dealing with structural studies and the practical uses of organosilicon compounds. 1. The “Theory” part of the book opens with “Nonclassical Organosilicon Compounds,” a contribution from Olga Gapurenko, Ruslan Minyaev, and Vladimir Minkin (Southern Federal University, Rostov-on-Don, Russian Federation). In this chapter, the authors discuss state-of-the-art computational approaches to the emerging field of nonstandard (so-called nonclassical) organosilicon compounds with unusual bonding situations (pyramidal structures featuring inverted tetrahedral silicon, sandwich complexes, hypercoordinate and high-spin systems) that classical bonding theory fails to adequately describe. 2. The “Experiment” part of the book deals with the most spectacular experimental advances in the field of synthetic and structural studies and is divided into two large xv xvi Preface sections, “Synthesis” and “Physico-Chemical Studies.” The “Synthesis” section is further divided into three subsections, in accordance with the coordination number of the central silicon: normal tetracoordinate, low-coordinate, and hypercoordinate. The first subsection, “Organosilicon Compounds of Tetracoordinate Silicon,” has three contributions on the hot topics of transition metal complexes featuring silyl ligands, organosilicon clusters, and chiral organosilicon compounds. Makoto Tanabe and Kohtaro Osakada (Tokyo Institute of Technology, Yokohama, Japan), the authors of the chapter “Transition Metal Complexes of Silicon,” comprehensively cover those featuring single bonds between the silicon and transition metals (both late and early). The following chapter, “Organosilicon Clusters,” authored by Soichiro Kyushin (Gunma University, Kiryu, Japan) describes a variety of cage, polyhedral, and ring catenation compounds, as well as spirooligosilanes, and siliconoids: their synthesis, structural studies, and specific reactivity. In his chapter, “Chiral Organosilicon Compounds,” Li-Wen Xu (Hangzhou Normal University, Hangzhou, China) discusses advances in the synthesis of silicon-stereogenic compounds and their application in asymmetric synthesis. The focus of the second subsection, “Organosilicon Compounds of Low-Coordinate Silicon,” is the flourishing field of studies on the silicon analogues of pivotal organic chemistry reactive intermediates, namely, silicon-centered cations, radicals, and anions, as well as silylenes, multiply bonded silicon compounds, and silaaromatics. In the first contribution in this subsection, “Silicon-Centered Cations,” Vladimir Lee and Akira Sekiguchi (University of Tsukuba, Tsukuba, Japan) provide a picture of the tricoordinate cations with a central six-valence-electron cationic silicon in the 1IV oxidation state (so- called silylium ions): general synthetic approaches for their generation, structural studies (NMR spectroscopy, X-ray crystallography), and the application of silylium ions in organic synthesis. Discussing silyl radicals (in the chapter “Silicon-Centered Radicals”), Boris Tumanskii, Miriam Karni, and Yitzhak Apeloig (Technion—Israel Institute of Technology, Haifa, Israel) focus on persistent and stable representatives with a particular emphasis on a group of polysilyl radicals and EPR spectroscopy as a major tool for identification and investigation of free radical species. Silyl anions is the subject of the next contribution, “Silicon-Centered Anions,” by Christoph Marschner (Graz University of Technology, Graz, Austria), in which the author gives an overview of a variety of anionic silicon derivatives, including the rather promising functionalized silyl anions, silyl dianions, delocalized silyl anions, as well as compounds with a negative charge centered on the sp2-Si atoms. Shintaro Ishida and Takeaki Iwamoto (Tohoku University, Sendai, Japan), in their contribution, “Stable Silylenes and Their Transition Metal Complexes,” continue the story of the low- coordinate silicon derivatives, comprehensively covering recent progress in the emerging field of stable silylenes: their synthesis, structural studies, and use as ligands for transition metal complexes. One of the most challenging topics of contemporary organosilicon chemistry, multiply-bonded derivatives, is overviewed by Antoine Baceiredo and Tsuyoshi Preface xvii Kato (Universite´ de Toulouse, Toulouse, France) in their chapter, “Multiple Bonds to Silicon.” They summarize the latest developments in the field of doubly and triply bonded silicon compounds, both homonuclear and heteronuclear. The “Low-Coordinate Silicon” subsection is completed by a contribution from Yoshiyuki Mizuhata and Norihiro Tokitoh (Kyoto University, Kyoto, Japan), “Silaaromatics and Related Compounds,” in which the authors discuss the peculiar properties of silaaromatic compounds, both neutral and charged, as well as those of their transition metal complexes. The Synthesis section ends with the subsection “Organosilicon Compounds of Hypercoordinate Silicon.” In his chapter, “Penta- and Hexacoordinated Silicon (IV) Compounds,” Naokazu Kano (University of Tokyo, Tokyo, Japan) classifies the title derivatives based on the type of element bound to the silicon, as well as the type of ligand at the silicon center. Successful preparation of organosilicon compounds, as described in the “Synthesis” section, requires subsequent structural studies, and overviews of such techniques are summarized in the “Physico-Chemical Studies” section of the experimental part of the book. It comprises four contributions dealing with the major state-of-the-art instrumental methods for assessing the structures of organosilicon derivatives. The first one, “X-Ray Crystallography of Organosilicon Compounds,” written by Niepo¨tter Benedikt and Dietmar Stalke (University of Go¨ttingen, Go¨ttingen, Germany), provides a fresh look into the nature of chemical bonding based on experimental and computational studies of electron density distribution. 29Si NMR spectroscopy is a major tool for the study of organosilicon compounds in solutions, and Frank Uhlig (Graz University of Technology, Graz, Austria) in his contribution “29Si NMR Spectroscopy” deals with the general features of this spectroscopic technique, emphasizing particular aspects of the range of silicon nuclei resonances, spin-spin coupling constants, and 29Si NMR pulse techniques. In the next chapter, “Thermochemistry of Organosilicon Compounds,” Rosa Becerra and Robin Walsh (University of Reading, Reading, U.K.) reviews, updates, and evaluates enthalpies of formation along with bond dissociation enthalpies for a range of organosilicon compounds, with solid support from theoretical calculations. The chapter “UV-Photoelectron Spectroscopy of Organosilicon Compounds,” by Anna Chrostowska and Clovis Darrigan (Universite´ de Pau et des Pays de l’Adour, Pau, France), completes the physico-chemical section, describing the advantages of UV-photoelectron spectroscopy (UV-PES) as a powerful tool in the study of the electronic structure of organosilicon compounds (as a special bonus for nonspecialized readers, basic information on UV-PES fundamentals and theoretical methods for the evaluation of ionization energies are also provided). As the culmination of all research efforts, the final part of the book Applications reports on the practical uses of organosilicon compounds in synthetic chemistry directed toward the xviii Preface creation of new materials. In the first contribution, “Hydrosilylation of the Carbon-Carbon Multiple Bonds,” Bogdan Marciniec, Hieronim Maciejewski, and Piotr Pawluc´ (Adam Mickiewicz University, Poznan´, Poland) give an account of recent developments in catalytic hydrosilylation of alkenes and alkynes as one of the most important methods for preparation of organosilicon compounds such as alkenylsilanes, particularly stressing the use of hydrosilylation for the production of silicones, ceramics, and nanocomposites. In the next chapter, “Polysilanes,” Julian Koe and Michiya Fujiki (International Christian University, Tokyo, Japan) comprehensively cover different aspects of the chemistry of polysilanes, discussing their structures and electronic properties, synthetic approaches, functionalization, and their high-end applications as chemical sensors and devices (photovoltaic devices, organic light-emitting diodes). Dimitris Katsoulis, Randall Schmidt, and Gregg Zank (Dow Corning Corporation, Midland, USA), in their chapter, “Siloxanes and Silicones,” discuss the production, specific properties, and ubiquitous application of silicones as one of the most popular silicon-based synthetic polymers, widely applied in various industrial fields (transportation, construction, fabrication of optoelectronic devices, healthcare applications). In the very final contribution of the Applications section, “Organosilicon Dendrimers and Irregular Hyperbranched Polymers,” Aziz Muzafarov, Elena Tatarinova, Nataliya Vasilenko, and Galina Ignat’eva (A. N. Nesmeyanov Institute of Organoelement Compounds, Moscow, Russian Federation) present a complete picture of the silicon-based dendrimers and hyperbranched polymers, macromolecular nano-objects that have found widespread application as functional materials for photonics, optoelectronics, ceramics, catalytic and drug delivery systems. As editor, I am very grateful to all these authors, whose excellent contributions, I hope, make this book a useful reference source and guide to contemporary organosilicon chemistry, further inspiring those working in the field. And though the book is first and foremost addressed to those working in the fascinating and challenging fields of organosilicon and organometallic chemistry, it could also be of interest to and useful for both main group and transition metal chemistry specialists, material science experts, and the rest of the chemical community. Vladimir Ya. Lee Tsukuba, Japan March 2017 CHAPTER 1 X-Ray Crystallography of Organosilicon Compounds (Electron Density and Chemical Bonding in Organosilicon Compounds) Benedikt Niepo¨tter and Dietmar Stalke University of G¨ottingen, G¨ottingen, Germany Chapter Outline 1.1 Introduction 3 1.1.1 MultipoleModel 5 1.1.2 FurtherModels 6 1.1.3 ExtractingBondingFeaturesFromtheEDD 6 1.2 The Natureof the Si-X Bond 9 1.3 Aromaticity in Silicon-Containing Compounds 14 1.3.1 Three-MemberedRings 15 1.3.2 Four-MemberedRings 18 1.3.3 Five-MemberedRings 21 1.3.4 Six-MemberedRings 24 1.4 Multiple Bondsand Low-Valent Silicon 30 1.4.1 MultipleBonds 30 1.4.2 Silylenes 34 1.4.3 SilaallenesandSilylones 40 1.5 Conclusions 46 References 47 Further Reading 58 1.1 Introduction The structure of a compound, composed from the various atom types and the divers bonding, determines its reactivity and properties.1 This fact probably makes the electron density one of the most informative observables of natural sciences. Since X-rays are mainly scattered by electrons X-ray diffraction techniques provide one of the most powerful OrganosiliconCompounds. 3 DOI:http://dx.doi.org/10.1016/B978-0-12-814213-4.00001-0 ©2017ElsevierInc.Allrightsreserved.
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