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Structure of disilene, the simplest silene Disilene-2D.svg
Structure of disilene, the simplest silene

Silene, or disilalkenes, [1] are silicon compounds that contain Si=Si double bonds. The parent silene is (the parent molecule) is disilene, Si



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. [2] [3] It was prepared by UV-photolysis of the related cyclic trisilane:

2 [Si(mesityl)2]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-bending of the substituents, which is never observed in alkenes. The trans-bent angles of disilenes between the R2Si planes and the Si=Si vector range from 0 to 33.8 °. This distortion is rationalized by the stability of the corresponding silylene fragments, although disilenes do not typically dissociate.

The distorted geometry of disilenes can be rationalized by considering the valence orbitals of silicon, which are 3s and 3p, whereas those of carbon are 2s and 2p. Thus, the energy gap between the ns and np orbitals of a silicon atom is larger than that of a carbon atom. Therefore, silylene fragments are in a singlet state, while carbene fragments are in a triplet state. So, when double bonds are formed by the interaction of these two fragments, disilenes which consist of two silylene units are trans-bending and alkenes which consist of two carbene units are planar. The bending is even more extreme for the tin analogues of disilenes. [1]


Disilenes are generally synthesized by reduction of 1,2-dihalodisilane, by retro-Diels–Alder fragmentation, by dimerization of silylenes, by photofragmentation of cyclopolysilanes, or by rearrangement of silylsilylenes.

A series of 1,1,1,4,4,4-hexaalkyl-2,3-bis(trialkylsilyl)tetrasil-2-enes structural analogues are typically synthesised using reductive coupling of the corresponding 1,1,1,3,3,3-hexaalkyl-2,3-tribromotrisilanes.

IUPAC names

To form the root of the IUPAC names for silenes, simply change the -an- infix of the parent to -en-. For example, SiH
is the silane disilANe. The name of SiH
is therefore disilENe.

In higher silenes, where isomers exist that differ in location of the double bond, the following numbering system is used:

  1. Number the longest silicon chain that contains the double bond in the direction that gives the silicon atoms of the double bond the lowest possible numbers.
  2. Indicate the location of the double bond by the location of its first silicon.
  3. Name branched or substituted silenes in a manner similar to silanes.
  4. Number the silicon atoms, locate and name substituent groups, locate the double bond, and name the main chain.

See also

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In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.

<i>Cis</i>–<i>trans</i> isomerism Pairs of molecules with same chemical formula showing different spatial orientations

Cistrans isomerism, also known as geometric isomerism or configurational isomerism, is a term used in chemistry that concerns the spatial arrangement of atoms within molecules. The prefixes "cis" and "trans" are from Latin: "this side of" and "the other side of", respectively. In the context of chemistry, cis indicates that the functional groups (substituents) are on the same side of some plane, while trans conveys that they are on opposing (transverse) sides. Cistrans isomers are stereoisomers, that is, pairs of molecules which have the same formula but whose functional groups are in different orientations in three-dimensional space. Cis-trans notation does not always correspond to EZ isomerism, which is an absolute stereochemical description. In general, cistrans stereoisomers contain double bonds that do not rotate, or they may contain ring structures, where the rotation of bonds is restricted or prevented. Cis and trans isomers occur both in organic molecules and in inorganic coordination complexes. Cis and trans descriptors are not used for cases of conformational isomerism where the two geometric forms easily interconvert, such as most open-chain single-bonded structures; instead, the terms "syn" and "anti" are used.

<span class="mw-page-title-main">Double bond</span> Chemical bond involving four bonding electrons; has one sigma plus one pi bond

In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist between two different elements: for example, in a carbonyl group between a carbon atom and an oxygen atom. Other common double bonds are found in azo compounds (N=N), imines (C=N), and sulfoxides (S=O). In a skeletal formula, a double bond is drawn as two parallel lines (=) between the two connected atoms; typographically, the equals sign is used for this. Double bonds were first introduced in chemical notation by Russian chemist Alexander Butlerov.

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">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">Carbon chauvinism</span> Scientific theory

Carbon chauvinism is a neologism meant to disparage the assumption that the chemical processes of hypothetical extraterrestrial life must be constructed primarily from carbon because as far as we know, carbon's chemical and thermodynamic properties render it far superior to all other elements at forming molecules used in living organisms.

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

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.

A silylenoid in organosilicon chemistry is a type of chemical compound with the general structure R2SiXM where R is any organic residue, X a halogen and M a metal. Silylenoids are the silicon pendants of carbenoid and both compounds have carbene or silylene like properties.

<span class="mw-page-title-main">Binary silicon-hydrogen compounds</span>

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, SiH
, the analogue of methane, continuing with disilane Si
, the analogue of ethane, etc. They are mainly of theoretical or academic interest.

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

Disilyne is a silicon hydride with the formula Si
. 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.

Carbene analogs in chemistry are carbenes with the carbon atom replaced by another chemical element. Just as regular carbenes they appear in chemical reactions as reactive intermediates and with special precautions they can be stabilized and isolated as chemical compounds. Carbenes have some practical utility in organic synthesis but carbene analogs are mostly laboratory curiosities only investigated in academia. Carbene analogs are known for elements of group 13, group 14, group 15 and group 16.

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">Disilene</span> Chemical compound

Disilene is an inorganic compound with the chemical formula Si
. The name disilene, referring to the structure of a particular prototropic tautomer of the molecule. It is the simplest silene.

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.

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

Stannylenes (R2Sn:) are a class of organotin(II) compounds that are analogues of carbene. Unlike carbene, which usually has a triplet ground state, stannylenes have a singlet ground state since valence orbitals of tin (Sn) have less tendency to form hybrid orbitals and thus the electrons in 5s orbital are still paired up. Free stannylenes are stabilized by steric protection. Adducts with Lewis bases are also known.

<span class="mw-page-title-main">Trisilaallene</span> Class of silicon chemical compounds

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.

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

Phosphasilenes or silylidenephosphanes are a class of compounds with silicon-phosphorus double bonds. Since the electronegativity of phosphorus (2.1) is higher than that of silicon (1.9), the "Si=P" moiety of phosphasilene is polarized. The degree of polarization can be tuned by altering the coordination numbers of the Si and P centers, or by modifying the electronic properties of the substituents. The phosphasilene Si=P double bond is highly reactive, yet with the choice of proper substituents, it can be stabilized via donor-acceptor interaction or by steric congestion.

<i>N</i>-heterocyclic silylene Chemical compound

An N-Heterocyclic silylene (NHSi) is an uncharged heterocyclic chemical compound consisting of a divalent silicon atom bonded to two nitrogen atoms. The isolation of the first stable NHSi, also the first stable dicoordinate silicon compound, was reported in 1994 by Michael Denk and Robert West three years after Anthony Arduengo first isolated an N-heterocyclic carbene, the lighter congener of NHSis. Since their first isolation, NHSis have been synthesized and studied with both saturated and unsaturated central rings ranging in size from 4 to 6 atoms. The stability of NHSis, especially 6π aromatic unsaturated five-membered examples, make them useful systems to study the structure and reactivity of silylenes and low-valent main group elements in general. Though not used outside of academic settings, complexes containing NHSis are known to be competent catalysts for industrially important reactions. This article focuses on the properties and reactivity of five-membered NHSis.

Silanes refers to diverse kinds of charge-neutral silicon compounds with the formula SiR4. The R substituents can any combination of organic or inorganic groups. Most silanes contain Si-C bonds, and are discussed under organosilicon compounds.

<i>N</i>-Heterocyclic carbene boryl anion Isoelectronic structure

An N-heterocyclic carbene boryl anion is an isoelectronic structure of an N-heterocyclic carbene (NHC), where the carbene carbon is replaced with a boron atom that has a -1 charge. NHC boryl anions have a planar geometry, and the boron atom is considered to be sp2-hybridized. They serve as extremely strong bases, as they are very nucleophilic. They also have a very strong trans influence, due to the σ-donation coming from the boron atom. NHC boryl anions have stronger electron-releasing character when compared to normal NHCs. These characteristics make NHC boryl anions key ligands in many applications, such as polycyclic aromatic hydrocarbons, and more commonly low oxidation state main group element bonding.


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  3. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 363. ISBN   978-0-08-037941-8.