Binary silicon-hydrogen compounds

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Chemical structure of disilane, which is structurally similar to ethane. Disilane.png
Chemical structure of disilane, which is structurally similar to ethane.

Silanes are saturated chemical compounds with the empirical formula SixHy. They are hydrosilanes, a class of compounds that includes compounds with Si−H and other Si−X bonds. All contain tetrahedral silicon and terminal hydrides. They only have Si−H and Si−Si single bonds. The bond lengths are 146.0 pm for a Si−H bond and 233 pm for a Si−Si bond. The structures of the silanes are analogues of the alkanes, starting with silane, SiH4, the analogue of methane, continuing with disilane Si2H6, the analogue of ethane, etc. They are mainly of theoretical or academic interest. [1]

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Cyclopentasilane is structurally similar to cyclopentane, just larger. Pentasilolane.svg
Cyclopentasilane is structurally similar to cyclopentane, just larger.

The simplest isomer of a silane is the one in which the silicon atoms are arranged in a single chain with no branches. This isomer is sometimes called the n-isomer (n for "normal", although it is not necessarily the most common). However the chain of silicon atoms may also be branched at one or more silicon atoms. The number of possible isomers increases rapidly with the number of silicon atoms. The members of the series (in terms of number of silicon atoms) follow:

Silanes are named by adding the suffix -silane to the appropriate numerical multiplier prefix. Hence, disilane, Si2H6; trisilane Si3H8; tetrasilane Si4H10; pentasilane Si5H12; etc. The prefix is generally Greek, with the exceptions of nonasilane which has a Latin prefix, and undecasilane and tridecasilane which have mixed-language prefixes. Solid phase polymeric silicon hydrides called polysilicon hydrides are also known. When hydrogen in a linear polysilene polysilicon hydride is replaced with alkyl or aryl side-groups, the term polysilane is used.

3-Silylhexasilane, H3Si−SiH2−SiH(−SiH3)−SiH2−SiH2−SiH3, is the simplest chiral binary noncyclic silicon hydride.

Cyclosilanes also exist. They are structurally analogous to the cycloalkanes, with the formula SinH2n, n > 2.

Data for small silanes [1]
SilaneFormulaMelting point [°C]Boiling point [°C]Density [g cm−3] (at 25 °C)Appearance
Silane SiH4−185−112Colorless gas
Disilane Si2H6−132−14Colorless gas
Trisilane Si3H8−117530.743Colorless liquid
Cyclotrisilane  [ el ]Si3H6
Tetrasilane  [ de; ru ]Si4H10−901080.793Colorless liquid
Pentasilane  [ de; ru ]Si5H12−72.81530.827Colorless liquid
Cyclopentasilane Si5H10−10.5[ clarification needed ]194[ clarification needed ]0.963Colorless liquid
Hexasilane  [ de; ru ]Si6H14−44.7193.60.847Colorless liquid

Production

Early work was conducted by Alfred Stock and Carl Somiesky. [2] Although monosilane and disilane were already known, Stock and Somiesky discovered, beginning in 1916, the next four members of the SinH2n+2 series, up to n = 6. They also documented the formation of solid phase polymeric silicon hydrides. [3] One of their synthesis methods involved the hydrolysis of metal silicides. This method produces a mixture of silanes, which required separation on a high vacuum line. [4] [5] [6]

The silanes (SinH2n+2) are less thermally stable than alkanes (CnH2n+2). They tend to undergo dehydrogenation, yielding hydrogen and polysilanes. For this reason, the isolation of silanes higher than heptasilane has proved difficult. [7]

The Schlesinger process is used to prepare silanes by the reaction of perchlorosilanes with lithium aluminium hydride.

Applications

The single but significant application for SiH4 is in the microelectronics industry. By metal organic chemical vapor deposition, silane is converted to silicon by thermal decomposition:

SiH4 → Si + 2 H2

Hazards

Silane is explosive when mixed with air (1 – 98% SiH4[ clarification needed ]). Other lower silanes can also form explosive mixtures with air. The lighter liquid silanes are highly flammable; this risk increases with the length of the silicon chain.

Considerations for detection/risk control:

Nomenclature

The IUPAC nomenclature (systematic way of naming compounds) for silanes is based on identifying hydrosilicon chains. Unbranched, saturated hydrosilicon chains are named systematically with a Greek numerical prefix denoting the number of silicons and the suffix "-silane".

IUPAC naming conventions can be used to produce a systematic name.

The key steps in the naming of more complicated branched silanes are as follows:

The nomenclature parallels that of alkyl radicals.

Silanes can also be named like any other inorganic compound; in this naming system, silane is named silicon tetrahydride. However, with longer silanes, this becomes cumbersome.

See also

Related Research Articles

<span class="mw-page-title-main">Alkane</span> Type of saturated hydrocarbon compound

In organic chemistry, an alkane, or paraffin, is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in which all the carbon–carbon bonds are single. Alkanes have the general chemical formula CnH2n+2. The alkanes range in complexity from the simplest case of methane, where n = 1, to arbitrarily large and complex molecules, like pentacontane or 6-ethyl-2-methyl-5-(1-methylethyl) octane, an isomer of tetradecane.

<span class="mw-page-title-main">Functional group</span> Set of atoms in a molecule which augment its chemical and/or physical properties

In organic chemistry, a functional group is a substituent or moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions regardless of the rest of the molecule's composition. This enables systematic prediction of chemical reactions and behavior of chemical compounds and the design of chemical synthesis. The reactivity of a functional group can be modified by other functional groups nearby. Functional group interconversion can be used in retrosynthetic analysis to plan organic synthesis.

<span class="mw-page-title-main">Silicon</span> Chemical element, symbol Si and atomic number 14

Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic table: carbon is above it; and germanium, tin, lead, and flerovium are below it. It is relatively unreactive.

Silane (Silicane) is an inorganic compound with chemical formula SiH4. It is a colourless, pyrophoric, toxic 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. Silane 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.

Silicon tetrachloride or tetrachlorosilane is the inorganic compound with the formula SiCl4. It is a colorless volatile liquid that fumes in air. It is used to produce high purity silicon and silica for commercial applications. It is a part of the chlorosilane family.

<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 shape 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".

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

Silene, or disilalkenes, are silicon compounds that contain Si=Si double bonds. The parent silene is is disilene, Si
2
H
4
.

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

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.

<span class="mw-page-title-main">Organosilicon chemistry</span> Organometallic compound containing carbon–silicon bonds

Organosilicon chemistry is the study of organometallic compounds containing carbon–silicon bonds, to which they are called organosilicon compounds. Most organosilicon compounds are similar to the ordinary organic compounds, being colourless, flammable, hydrophobic, and stable to air. Silicon carbide is an inorganic compound.

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 and Alfred Stock.

Hydrosilanes are tetravalent silicon compounds containing one or more Si-H bond. The parent hydrosilane is silane (SiH4). Commonly, hydrosilane refers to organosilicon derivatives. Examples include phenylsilane (PhSiH3) and triethoxysilane ((C2H5O)3SiH). Polymers and oligomers terminated with hydrosilanes are resins that are used to make useful materials like caulks.

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

Disilyne is a silicon hydride with the formula Si
2
H
2
. 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.

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.

Polysilicon halides are silicon-backbone polymeric solids. At room temperature, the polysilicon fluorides are colorless to yellow solids while the chlorides, bromides, and iodides are, respectively, yellow, amber, and red-orange. Polysilicon dihalides (perhalo-polysilenes) have the general formula (SiX2)n while the polysilicon monohalides (perhalo-polysilynes) have the formula (SiX)n, where X is F, Cl, Br, or I and n is the number of monomer units in the polymer.

<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">Digermane</span> Chemical compound

Digermane is an inorganic compound with the chemical formula Ge2H6. One of the few hydrides of germanium, it is a colourless liquid. Its molecular geometry is similar to ethane.

The dehydrogenative coupling of silanes is a reaction type for the formation of Si-Si bonds. Although never commercialized, the reaction has been demonstrated for the synthesis of certain disilanes as well as polysilanes. These reactions generally require catalysts.

Group 14 hydrides are chemical compounds composed of hydrogen atoms and group 14 atoms.

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

Cyclopentasilane is a cyclic compound of silicon and hydrogen with the chemical formula Si5H10. Containing five silicon atoms arranged in a pentagonal ring, it is the silicon analog of cyclopentane. Cyclopentasilane is a colorless pyrophoric liquid. It is an oligosilane. It is of research interest because of its potential use as a liquid silicon ink for printing silicon structures on integrated circuits or solar cells.

Silanes refers to diverse organosilicon charge-neutral compounds with the formula SiR
4
. The R substituents can any combination of organic or inorganic groups. Most silanes contain Si-C bonds, and are discussed under organosilicon compounds. Some contain Si-H bonds and are discussed under hydrosilanes.

References

  1. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  2. E. Wiberg, Alfred Stock and the Renaissance of Inorganic Chemistry," Pure Appl. Chem., Vol. 49 (1977) pp. 691-700.
  3. J. W. Mellor, "A Comprehensive Treatise on Inorganic and Theoretical Chemistry," Vol. VI, Longman, Green and Co. (1947) pp. 223 - 227.
  4. Hydrides of Boron and Silicon. Ithaca (USA) 1933.
  5. Stock, A.; Stiebeler, P.; Zeidler, F. (1923). "Siliciumwasserstoffe, XVI. Die höheren Siliciumhydride". Ber. Dtsch. Chem. Ges. B. 56B: 1695-1705. doi:10.1002/cber.19230560735.
  6. P. W. Schenk (1963). "Silanes SiH4 (Si2H6, Si3H8)". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY, NY: Academic Press. pp. 679–680.
  7. W. W. Porterfield "Inorganic Chemistry: A Unified Approach," Academic Press (1993) p. 219.