Hydrosilanes

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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.

Contents

Synthesis

Trichlorosilane is produced commercially by the reaction of hydrogen chloride with silicon:

Si + 3 HCl → HSiCl3 + H2

Many alkoxy hydrosilanes are generated by alcoholysis of trichlorosilane. One example is triethoxysilane:

HSiCl3 + 3 EtOH → HSi(OEt)3 + 3 HCl

Organohydrosilanes can be prepared by partial hydrosilation of silane itself:

SiH4 + 3 C2H4 → HSi(C2H5)3

In the laboratory, hydrosilanes classically are prepared by treating chlorosilanes with hydride reagents, such as lithium aluminium hydride:

4 ClSi(C2H5)3 + LiAlH4 → 4 HSi(C2H5)3 + LiAlCl4

Bonding and structure

The silicon-to-hydrogen bond is longer than the C–H bond (148 compared to 105 pm). The Si-H bond is about 10% weaker compared to C-H bonds.

Bond dissociation energies [1]
BondD
(kJ/mol, 298K)
H3C-H 441
H3Si-H 384
(CH3)3C-H 404
(CH3)3Si-H 397
((CH3)3Si)3Si-H 351

Hydrogen is more electronegative than silicon (hence the naming convention of silyl hydrides), which results in the polarization of the Si-H bond to be the reverse of that for the C-H bond. Generally silyl hydrides are colourless with physical properties (solubility, volatility) comparable to hydrocarbons. They can be pyrophoric, reflecting the great driving force for replacing Si-H bonds with Si-O bonds.

Reactions and applications

Setting aside silane itself, for which is used mainly in the microelectronics industry as a source of Si, hydrosilanes participate in many reactions. Hydrosilanes are mainly used for diverse styles of reduction in both industrial and laboratory-scale reactions. These including deoxygenation, hydrosilylation, and ionic hydrogenation.

Hydrosilylation

SIn hydrosilylation, the Si-H bond adds across multiple bonds in alkenes, alkynes, imines, and carbonyls. The reaction of alkenes is commercially significant. Many organosilicon compounds and materials are prepared in this way. Illustrative is the crosslinking of vinyl-terminated siloxanes:

Pt-catalyzed vulcanization of a siloxane resin VinylSi+HSi.png
Pt-catalyzed vulcanization of a siloxane resin

Conversion to silanols

In the presence of platinum-based catalysts, hydrosilanes react with water to give silanols:

R3SiH + H2O → R3SiOH + H2

The same transformation can be effected with oxygen in the presence of catalysts. [2]

Fluoride complexes

In the presence of fluoride ions, hydrosilanes reversibly form hypervalent fluorosilicates with the formula R3Si(F)H). These species are reducing agents, akin to borohydride. [3] [4]

HSMech2.png

Ionic hydrogenation

Reductions with hydrosilanes are a subset of ionic hydrogenations. In this type of reaction, carbocations are generated by the action of strong Lewis or Brønsted acids in the presence of hydrosilanes, which then transfer hydride. A typical acid is trifluoroacetic acid (TFA).

HSStereo1.png

The reaction is stoichiometric.

Deoxygenation and ionic hydrogenation

Hydrosilanes are used for the deoxygenation of phosphine oxides and sulfoxides. [5]

Hydrosilanes serve as hydride donors in some ionic hydrogenations.

HSEx.png

Coordination the metals

Hydrosilanes form sigma complexes with unsaturated metals. The bonding is similar to that in dihydrogen complexes but stronger. One example is (CH3C5H4)Mn(CO)2(H2SiPh2). [6] Such adducts represent models for and competitors with the oxidative addition of the Si-H bond.

Reduction of or addition to organic substrates

Akin to the hydrosilylation of alkenes, hydrosilanes add to a variety of unsaturated substrates.

In one example, PMHS. In one study triethylsilane is used in the conversion of a phenyl azide to an aniline: [7]

AzideReductionByTriethylsilylhydride.png

In this reaction ACCN is a radical initiator and an aliphatic thiol transfers radical character to the silylhydride. The triethylsilyl free radical then reacts with the azide with expulsion of nitrogen to a N-silylarylaminyl radical which grabs a proton from a thiol completing the catalytic cycle:

AzideReductionMechanism.png

Further reading

Selective reading

Related Research Articles

In chemistry, a hydride is formally the anion of hydrogen, H. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently 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.

Silane is an inorganic compound with chemical formula, SiH4. It is a colourless, pyrophoric, toxic gas with a sharp, repulsive 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.

Silanol Si–OH functional group in silicon chemistry

A silanol is a functional group in silicon chemistry with the connectivity Si–O–H. It is related to the hydroxy functional group (C–O–H) found in all alcohols. Silanols are often invoked as intermediates in organosilicon chemistry and silicate mineralogy. If a silanol contains one or more organic residue, it is an organosilanol.

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

Trimethylsilyl

A trimethylsilyl group (abbreviated TMS) is a functional group in organic chemistry. This group consists of three methyl groups bonded to a silicon atom [−Si(CH3)3], which is in turn bonded to the rest of a molecule. This structural group is characterized by chemical inertness and a large molecular volume, which makes it useful in a number of applications.

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.

Chloroplatinic acid Chemical compound

Chloroplatinic acid (also known as hexachloroplatinic acid) is an inorganic compound with the formula [H3O]2[PtCl6](H2O)x (0 ≤ x ≤ 6). A red solid, it is an important commercial source of platinum, usually as an aqueous solution. Although often written in shorthand as H2PtCl6, it is the hydronium (H3O+) salt of the hexachloroplatinate anion (PtCl2−
6
). Hexachloroplatinic acid is highly hygroscopic.

Organosilicon compound 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.

Binary silicon-hydrogen compounds

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
4
, the analogue of methane, continuing with disilane Si
2
H
6
, the analogue of ethane, etc. They are mainly of theoretical or academic interest.

Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds across unsaturated bonds. Ordinarily the reaction is conducted catalytically and usually the substrates are unsaturated organic compounds. Alkenes and alkynes give alkyl and vinyl silanes; aldehydes and ketones give silyl ethers. Hydrosilylation has been called the "most important application of platinum in homogeneous catalysis."

Reductions with hydrosilanes are methods used for hydrogenations and hydrogenolysis of organic compounds. The approach is a subset of Ionic hydrogenations. In this particular method, the substrate is treated with a hydrosilane and auxiliary reagent, often a strong acid, resulting in formal transfer of hydride from silicon to carbon. This style of reduction with hydrosilanes enjoys diverse if specialized applications.

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.

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.

Ionic Hydrogenation refers to hydrogenation achieved by the addition of a hydride to substrate that has been activated by an electrophile. Some ionic hydrogenations entail addition of H2 to the substrate and some entail replacement of a heteroatom with hydride. Traditionally, the method was developed for acid-induced reductions with hydrosilanes. Alternatively ionic hydrogenation can be achieved using H2. Ionic hydrogenation is employed when the substrate can produce a stable carbonium ion. Polar double bonds are favored substrates.

The Mukaiyama hydration is an organic reaction involving formal addition of an equivalent of water across an olefin by the action of catalytic bis(acetylacetonato)cobalt(II) complex, phenylsilane and atmospheric oxygen to produce an alcohol with Markovnikov selectivity.

Tris(trimethylsilyl)silane Chemical compound

Tris(trimethylsilyl)silane is the organosilicon compound with the formula (Me3Si)3SiH (where Me = CH3). It is a colorless liquid that is classified as a hydrosilane since it contains an Si-H bond. The compound is notable as having a weak Si-H bond, with a bond dissociation energy estimated at 84 kcal/mol. For comparison, the Si-H bond in trimethylsilane is 94 kcal/mol. With such a weak bond, the compound is used as a reagent to deliver hydrogen atoms. The compound has been described as an environmentally benign analogue of tributyltin hydride.

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.

Transition metal silane complexes

Transition metal silane complexes are coordination compounds containing hydrosilane ligands. An early example is (MeC5H4)Mn(CO)22-HSiPh3) (Ph = C6H5).

In chemistry, transition metal silyl complexes describe coordination complexes in which a transition metal is bonded to an anionic silyl ligand, forming a metal-silicon sigma bond. This class of complexes are numerous and some are technologically significant as intermediates in hydrosilylation.

A silanide is a chemical compound containing an anionic silicon(IV) centre, the parent ion being SiH−3. The hydrogen atoms can also be substituted to produced more complex derivative anions such as tris(trimethylsilyl)silanide (hypersilyl), tris(tert-butyl)silanide, tris(pentafluoroethyl)silanide, or triphenylsilanide. The simple silanide ion can also be called trihydridosilanide or silyl hydride.

References

  1. Chatgilialoglu, Chryssostomos (1995). "Structural and Chemical Properties of Silyl Radicals". Chemical Reviews. 95 (5): 1229–1251. doi:10.1021/cr00037a005.
  2. Jeon, Mina; Han, Junghoon; Park, Jaiwook (2012). "Catalytic Synthesis of Silanols from Hydrosilanes and Applications". ACS Catalysis. 2 (8): 1539–1549. doi:10.1021/cs300296x.
  3. Chuit, C.; Corriu, R. J. P.; Perz, R.; Reyé, C. Synthesis1982, 981.
  4. Fleck, T. J. "Phenylsilane–Cesium Fluoride". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rp101.
  5. Colvin, Ernest W. (1981). "Silanes as Reducing Agents". Silicon in Organic Synthesis. pp. 325–336. doi:10.1016/B978-0-408-10831-7.50027-5. ISBN   9780408108317.
  6. McGrady, G. Sean; Sirsch, Peter; Chatterton, Nicholas P.; Ostermann, Andreas; Gatti, Carlo; Altmannshofer, Sandra; Herz, Verena; Eickerling, Georg; Scherer, Wolfgang (2009). "Nature of the Bonding in Metal-Silane σ-Complexes". Inorganic Chemistry. 48 (4): 1588–1598. doi:10.1021/ic8019777. PMID   19146446. S2CID   40616439.
  7. Benati, Luisa; Bencivenni, Giorgio; Leardini, Rino; Minozzi, Matteo; Nanni, Daniele; Scialpi, Rosanna; Spagnolo, Piero; Zanardi, Giuseppe (2006). "Radical Reduction of Aromatic Azides to Amines with Triethylsilane". J. Org. Chem. 71 (15): 5822–5825. doi:10.1021/jo060824k. PMID   16839176.