Polysilyne

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In organosilicon chemistry, polysilynes are chemical compounds with the formula [RSi]n, where R can be hydrogen (e.g. in polysilyne [HSi]n), or organyl (e.g. in poly(methylsilyne)). Although their name suggests a relationship to alkynes (−C≡C−), polysilynes are a class of silicon-based random network polymers primarily composed of tetrahedral silicon atoms, each connected to one hydrogen or carbon and three Si atoms. These compounds are prepared by Wurtz coupling of alkyltrichlorosilanes (RSiCl3):

3 Na + RSiCl3[RSi]n + 3 NaCl

The methyl and hexyl derivatives have been described. [1] Poly(methylsilyne) (PMSy) [CH3Si]n is a dark yellow powder. [2] With some solvents (tetrahydrofuran, ether, toluene etc.) it forms a colloidal suspension that is clear and non-viscous, which may then be deposited as a film or coating on various substrates.

Poly(methylsilyne) is a preceramic polymer, converting to silicon carbide upon thermolysis in an inert atmosphere. The optical properties of these materials has attracted attention. [3]

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<span class="mw-page-title-main">Metallocene</span> Type of compound having a metal center

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen ion with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and more frequently in the past) been applied to all compounds containing covalently bound H atoms. In this broad and potentially archaic sense, water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. In covalent compounds, it implies hydrogen is attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

<span class="mw-page-title-main">Silane</span> Chemical compound (SiH4)

Silane (Silicane) is an inorganic compound with chemical formula SiH4. It is a colorless, pyrophoric gas with a sharp, repulsive, pungent smell, somewhat similar to that of acetic acid. Silane is of practical interest as a precursor to elemental silicon. Silanes with alkyl groups are effective water repellents for mineral surfaces such as concrete and masonry. Silanes with both organic and inorganic attachments are used as coupling agents. They are commonly used to apply coatings to surfaces or as an adhesion promoter.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) HC≡CH by metallic or other cations. Calcium carbide is an important industrial compound, which has long been used to produce acetylene for welding and illumination. It is also a major precursor to vinyl chloride. Other acetylides are reagents in organic synthesis.

<span class="mw-page-title-main">Organotin chemistry</span> Branch of organic chemistry

Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin–carbon bonds. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849. The area grew rapidly in the 1900s, especially after the discovery of the Grignard reagents, which are useful for producing Sn–C bonds. The area remains rich with many applications in industry and continuing activity in the research laboratory.

<span class="mw-page-title-main">Siloxane</span> Organic functional group (Si–O–Si)

In organosilicon chemistry, a siloxane is an organic compound containing a functional group of two silicon atoms bound to an oxygen atom: Si−O−Si. The parent siloxanes include the oligomeric and polymeric hydrides with the formulae H[OSiH2]nOH and [OSiH2]n. Siloxanes also include branched compounds, the defining feature of which is that each pair of silicon centres is separated by one oxygen atom. The siloxane functional group forms the backbone of silicones [−R2Si−O−SiR2−]n, the premier example of which is polydimethylsiloxane (PDMS). The functional group R3SiO− is called siloxy. Siloxanes are manmade and have many commercial and industrial applications because of the compounds’ hydrophobicity, low thermal conductivity, and high flexibility.

In inorganic chemistry, chlorosilanes are a group of reactive, chlorine-containing chemical compounds, related to silane and used in many chemical processes. Each such chemical has at least one silicon-chlorine bond. Trichlorosilane is produced on the largest scale. The parent chlorosilane is silicon tetrachloride.

<span class="mw-page-title-main">Borazine</span> Boron compound

Borazine, also known as borazole, inorganic benzene, is an inorganic compound with the chemical formula B3H6N3. In this cyclic compound, the three BH units and three NH units alternate. The compound is isoelectronic and isostructural with benzene. For this reason borazine is sometimes referred to as “inorganic benzene”. Like benzene, borazine is a colourless liquid with an aromatic odor.

<span class="mw-page-title-main">Parylene</span> Chemical compound

Parylene is the common name of a polymer whose backbone consists of para-benzenediyl rings −C
6
H
4
− connected by 1,2-ethanediyl bridges −CH
2
CH
2
−. It can be obtained by polymerization of para-xylyleneH
2
C
=C
6
H
4
=CH
2
.

<span class="mw-page-title-main">Hexachlorophosphazene</span> Chemical compound

Hexachlorophosphazene is an inorganic compound with the chemical formula (NPCl2)3. The molecule has a cyclic, unsaturated backbone consisting of alternating phosphorus and nitrogen atoms, and can be viewed as a trimer of the hypothetical compound N≡PCl2. Its classification as a phosphazene highlights its relationship to benzene. There is large academic interest in the compound relating to the phosphorus-nitrogen bonding and phosphorus reactivity.

Dimethyldichlorosilane is a tetrahedral organosilicon compound with the formula Si(CH3)2Cl2. At room temperature it is a colorless liquid that readily reacts with water to form both linear and cyclic Si-O chains. Dimethyldichlorosilane is made on an industrial scale as the principal precursor to dimethylsilicone and polysilane compounds.

<span class="mw-page-title-main">Methyltrichlorosilane</span> Chemical compound

Methyltrichlorosilane, also known as trichloromethylsilane, is a monomer and organosilicon compound with the formula CH3SiCl3. It is a colorless liquid with a sharp odor similar to that of hydrochloric acid. As methyltrichlorosilane is a reactive compound, it is mainly used a precursor for forming various cross-linked siloxane polymers.

<span class="mw-page-title-main">Digallane</span> Chemical compound

Digallane is an inorganic compound with the chemical formula GaH2(H)2GaH2. It is the dimer of the monomeric compound gallane. The eventual preparation of the pure compound, reported in 1989, was hailed as a "tour de force." Digallane had been reported as early as 1941 by Wiberg; however, this claim could not be verified by later work by Greenwood and others. This compound is a colorless gas that decomposes above 0 °C.

<span class="mw-page-title-main">Silsesquioxane</span> Molecular compound with applications in ceramics

A silsesquioxane is an organosilicon compound with the chemical formula [RSiO3/2]n. Silsesquioxanes are colorless solids that adopt cage-like or polymeric structures with Si-O-Si linkages and tetrahedral Si vertices. Silsesquioxanes are members of polyoctahedral silsesquioxanes ("POSS"), which have attracted attention as preceramic polymer precursors to ceramic materials and nanocomposites. Diverse substituents (R) can be attached to the Si centers. The molecules are unusual because they feature an inorganic silicate core and an organic exterior. The silica core confers rigidity and thermal stability.

In organosilicon chemistry, polysilazanes are polymers in which silicon and nitrogen atoms alternate to form the basic backbone. Since each silicon atom is bound to two separate nitrogen atoms and each nitrogen atom to two silicon atoms, both chains and rings of the formula [R2Si−NR]n occur. R can be hydrogen atoms or organic substituents. If all substituents R are hydrogen atoms, the polymer is designated as perhydropolysilazane, polyperhydridosilazane, or inorganic polysilazane ([H2Si−NH]n). If hydrocarbon substituents are bound to the silicon atoms, the polymers are designated as Organopolysilazanes. Molecularly, polysilazanes [R2Si−NH]n are isoelectronic with and close relatives to polysiloxanes [R2Si−O]n (silicones).

Polysilicon hydrides are polymers containing only silicon and hydrogen. They have the formula where 0.2 ≤ n ≤ 2.5 and x is the number of monomer units. The polysilicon hydrides are generally colorless or pale-yellow/ocher powders that are easily hydrolyzed and ignite readily in air. The surfaces of silicon prepared by MOCVD using silane (SiH4) consist of a polysilicon hydride.

<span class="mw-page-title-main">Polysilane</span>

Polysilanes are organosilicon compounds with the formula (R2Si)n. They are relatives of traditional organic polymers but their backbones are composed of silicon atoms. They exhibit distinctive optical and electrical properties. They are mainly used as precursors to silicon carbide. The simplest polysilane would be (SiH2)n, which is mainly of theoretical, not practical interest.

<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (British and IUPAC spellings) or aluminum (North American spelling) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

References

  1. Bianconi, Patricia A.; Weidman, Timothy W. (1988). "Poly(n-hexylsilyne) synthesis and properties of the first alkyl silicon [RSi]n network polymer". J. Am. Chem. Soc. 110: 2342–2344. doi:10.1021/ja00215a077.
  2. U.S. patent 6,989,428 "Methods of preparing polysilynes"
  3. Brus, Louis (1994). "Luminescence of Silicon Materials: Chains, Sheets, Nanocrystals, Nanowires, Microcrystals, and Porous Silicon". Journal of Physical Chemistry. 98: 3575–81. doi:10.1021/j100065a007.