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Silenes
Silene, or disilalkenes,Philip P. Power "pi-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements" Chemical Reviews, 1999, 99, 3462. are silicon compounds that contain Si=Si double bonds. The parent silene is (the parent molecule) is disilene, . Structure The first transient disilene was reported in 1972 by D. N. Roark and Garry J. D. Peddle. Simple disilenes easily polymerize. To suppress this tendency, bulky substituents are used. Indeed the first isolable disilene, tetramesityldisilene, was described in 1981 by West, Fink, and Michl. It was prepared by UV-photolysis of the related cyclic trisilane: : 2 i(mesityl)2sub>3 → 3 (mesityl)2Si=Si(mesityl)2 Structure of tetramesityldisilene tetramesityldisilene is a yellow-orange solid. The Si=Si double bond lengths of disilenes vary between 2.14 and 2.29 Å and are nearly 5 to 10% shorter than the Si-Si single bond lengths of corresponding disilanes. A peculiarity of disilenes is the ''trans' ...
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Organosilicon
Organosilicon compounds are organometallic compounds containing carbon–silicon bonds. Organosilicon chemistry is the corresponding science of their preparation and properties. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an ''inorganic'' compound. History In 1846 Von Ebelman's had synthesized Tetraethyl orthosilicate (Si(OC2H5)4). In 1863 Friedel and Crafts managed to make the first organosilieon compound with C-Si bonds which gone byound the syntheses of orthosilicic acid esters. The same year they also described a «polysilicic acid ether» in the preparation of ethyl- and methyl-o-silicic acid. The early extensive research in the field of organosilicon compounds was pioneerd in the beginning of 20th century by Frederic Kipping. He also had coined the term «silicone» (akin to ketones) in relation to these materials in 1904. In recognition of Kipping's achiev ...
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Trisilaallene
Trisilaallene is a subclass of silene derivatives where a central silicon atom forms double bonds with each of two terminal silicon atoms, with the generic formula R2Si=Si=SiR2. Trisilaallene is a silicon-based analog of an allene, but their chemical properties are markedly different. Synthesis The first isolable trisilaallene compound was reported by Kira ''et al.'' in 2003, synthesized by reductive dehalogenation of tetrachlorosilane using potassium graphite. This tetraalkyl-substituted trisilallene showed thermal stability up to its melting point around 200 °C, but decomposed in contact with air. Its remarkable stability is attributable to bulky substituents providing kinetic protection at the terminal silicon atoms. The 29Si- NMR shifts of the central silicon and terminal silicon atoms were observed at 157.0 ppm and 196.9 ppm respectively. Two Si=Si bond lengths were determined to be 2.177 Å and 2.188 Å by X-ray crystallography, which are within the typical range of ...
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Robert West (chemist)
Robert Culbertson West Jr. (March 18, 1928 – October 12, 2022) was an American chemist. West was an E. G. Rochow Professor of Chemistry Emeritus at the University of Wisconsin–Madison; Director of the Organosilicon Research Center, University of Wisconsin–Madison 1999–20??; President, Silatronix, Inc. (2007–20??); Distinguished Professor, Yonsei University, 2007–2011. He died in Madison, Wisconsin on October 12, 2022, at the age of 94. Education West received his Bachelor of Arts in Chemistry from Cornell University in 1950, proceeding on to Harvard University where he received his Master of Arts in 1952 and Ph.D. in 1954. At Cornell, he was a member of the Quill and Dagger society. Notable work West was a chemist best known for his groundbreaking research in silicon chemistry as well as for his work with oxocarbons and organolithium compounds. In 2004, West was listed as one of the most cited scientists during the period 1981-1999, according to a citation surve ...
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Silanes
Silanes refers to diverse kinds of charge-neutral silicon compounds with the formula . The R substituents can any combination of organic or inorganic groups. Most silanes contain Si-C bonds, and are discussed under organosilicon compounds. Examples: *Silane , the parent. *Binary silicon-hydrogen compounds (which are sometimes called silanes also) includes silane itself but also compounds with Si-Si bonds including disilane and longer chains. *Silanes with one, two, three, or four Si-H bonds are called hydrosilanes. Silane itself is the parent member. Examples: triethylsilane () and triethoxysilane (). *Polysilanes are organosilicon compounds with the formula . They include all binary silicon-hydrogen compounds except the parent, although these tend to be less useful because they are fragile. Attracting more interest, are the organic derivatives such as polydimethylsilane and dodecamethylcyclohexasilane *Chlorosilanes have Si-Cl bonds. Examples: trichlorosilane () and tetrachlo ...
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Silylene
Silylene is a chemical compound with the formula SiH2. It is the silicon analog of methylene, the simplest carbene. Silylene is a stable molecule as a gas but rapidly reacts in a bimolecular manner when condensed. Unlike carbenes, which can exist in the singlet or triplet state, silylene (and all of its derivatives) are singlets. Silylenes are formal derivatives of silylene with its hydrogens replaced by other substituents. Most examples feature amido (NR2) or alkyl/aryl groups. Silylenes have been proposed as reactive intermediates. They are carbene analogs. Synthesis and properties Silylenes are generally synthesized by thermolysis or photolysis of polysilanes, by silicon atom reactions ( insertion, addition or abstraction), by pyrolysis of silanes, or by reduction of 1,1-dihalosilane. It has long been assumed that the conversion of metallic Si to tetravalent silicon compounds proceeds via silylene intermediates: :Si + Cl2 → SiCl2 :SiCl2 + Cl2 → SiCl4 Similar cons ...
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Diradical
In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate. The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and in fact rarely isolated. Diradicals are even-electron molecules but have one fewer bond than the number permitted by the octet rule. Examples of diradical species can also be found in coordination chemistry, for example among bis(1,2-dithiolene) metal complexes. Spin states Diradicals are usually triplets. The phrases ''singlet'' and ''triplet'' are derived from the multiplicity of states of diradicals in electron spin resonance: a singlet diradical has one state (S = 0, Ms = 2*0+1 = 1, ms = 0) and exhibits no signal in EPR and a triplet diradical has 3 states (S = 1, Ms = 2*1+1 = 3, ms = -1; 0; 1) and shows in EPR 2 peaks (if no hyperfine splitting). The triplet state has total spin quantum number S = 1 and is paramagnetic. Therefore, di ...
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Double Bond Rule
In chemistry, the double bond rule states that elements with a principal quantum number greater than 2 for their valence electrons (period 3 elements and higher) tend not to form multiple bonds (e.g. double bonds and triple bonds). The double bonds, when they exist, are often weak due to poor orbital overlap. Although such compounds are not intrinsically unstable, they instead tend to polymerize. An example is the rapid polymerization that occurs upon condensation of disulfur, the heavy analogue of . Numerous violations to the rule exist. Other meanings Another unrelated double bond rule exists that relates to the enhanced reactivity of sigma bonds attached to an atom adjacent to a double bond. In bromoalkenes, the C–Br bond is very stable, but in an allyl bromide, this bond is very reactive. Likewise, bromobenzenes are generally inert, whereas benzylic bromides are reactive. The first to observe the phenomenon was Conrad Laar Conrad Peter Laar (22 March 1853 – 11 Fe ...
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Disilyne
Disilyne is a silicon hydride with the formula . Several isomers are possible, but none are sufficiently stable to be of practical value. Substituted disilynes contain a formal silicon–silicon triple bond and as such are sometimes written R2Si2 (where R is a substituent group). They are the silicon analogues of alkynes. The term ''silyne'' has two diverse meanings. Some chemists use it to refer to compounds containing a silicon–silicon triple bond,Egon Wiberg, Arnold Frederick Holleman (2001) ''Inorganic Chemistry'', Elsevier whereas others use the term to refer to compounds containing a silicon–carbon triple bond by analogy to silene, which often refers to compounds containing silicon–carbon double bonds. The term polysilyne can refer to the layer polymer (SiH)n or substituted derivatives. Substituted disilynes The first example isolated and characterised by X-ray crystallography is an emerald green crystalline compound reported in 2004. This molecule has the form ...
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Disilane
Disilane is a chemical compound with chemical formula Si2H6 that was identified in 1902 by Henri Moissan and Samuel Smiles (1877–1953). Moissan and Smiles reported disilane as being among the products formed by the action of dilute acids on metal silicides. Although these reactions had been previously investigated by Friedrich Woehler and Heinrich Buff between 1857 and 1858, Moissan and Smiles were the first to explicitly identify disilane. They referred to disilane as ''silicoethane''. Higher members of the homologous series SinH2n+2 formed in these reactions were subsequently identified by Carl Somiesky (sometimes spelled "Karl Somieski") and Alfred Stock. At standard temperature and pressure, disilane is a colourless, acrid gas. Disilane and ethane have similar structures, although disilane is much more reactive. Other compounds of the general formula Si2X6 (X = hydride, halide, alkyl, aryl, and mixtures of these groups) are called disilanes. Disilane is a group 14 hydrid ...
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Isomers
In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Isomers do not necessarily share similar chemical or physical properties. Two main forms of isomerism are structural or constitutional isomerism, in which ''bonds'' between the atoms differ; and stereoisomerism or spatial isomerism, in which the bonds are the same but the ''relative positions'' of the atoms differ. Isomeric relationships form a hierarchy. Two chemicals might be the same constitutional isomer, but upon deeper analysis be stereoisomers of each other. Two molecules that are the same stereoisomer as each other might be in different conformational forms or be different isotopologues. The depth of analysis depends on the field of study or the chemical and physical properties of interest. The English word "isomer" () is a back-form ...
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IUPAC Nomenclature
A chemical nomenclature is a set of rules to generate systematic names for chemical compounds. The nomenclature used most frequently worldwide is the one created and developed by the International Union of Pure and Applied Chemistry (IUPAC). The IUPAC's rules for naming organic and inorganic compounds are contained in two publications, known as the ''Blue Book''. . and the '' Red Book'',. respectively. A third publication, known as the '' Green Book'',. recommends the use of symbols for physical quantities (in association with the IUPAP), while a fourth, the ''Gold Book'',''Compendium of Chemical Terminology, IMPACT Recommendations (2nd Ed.)'', Oxford:Blackwell Scientific Publications. (1997) defines many technical terms used in chemistry. Similar compendia exist for biochemistry''Biochemical Nomenclature and Related Documents'', London: Portland Press, 1992. (the ''White Book'', in association with the IUBMB), analytical chemistry (the '' Orange Book''), macromolecular chemistr ...
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Dimer (chemistry)
A dimer () ('' di-'', "two" + ''-mer'', "parts") is an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. Dimers also have significant implications in polymer chemistry, inorganic chemistry, and biochemistry. The term ''homodimer'' is used when the two molecules are identical (e.g. A–A) and ''heterodimer'' when they are not (e.g. A–B). The reverse of dimerization is often called dissociation. When two oppositely charged ions associate into dimers, they are referred to as ''Bjerrum pairs'', after Niels Bjerrum. Noncovalent dimers Anhydrous carboxylic acids form dimers by hydrogen bonding of the acidic hydrogen and the carbonyl oxygen. For example, acetic acid forms a dimer in the gas phase, where the monomer units are held together by hydrogen bonds. Under special conditions, most OH-containing molecules form dimers, e.g. the water dimer. Excimers and exciplexes are excited structures with a short lifetime. ...
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