Silicon compounds

Silicon compounds are compounds containing the element silicon. As a carbon group element, silicon often forms compounds in the +4 oxidation state, though many unusual compounds have been discovered that differ from expectations based on its valence electrons, including the silicides and some silanes. Metal silicides, silicon halides, and similar inorganic compounds can be prepared by directly reacting elemental silicon or silicon dioxide with stable metals or with halogens. Silanes, compounds of silicon and hydrogen, are often used as strong reducing agents, and can be prepared from aluminium–silicon alloys and hydrochloric acid.
Several inorganic compounds have been formed with silicon and other nonmetals such as sulfur and nitrogen; most of these compounds are highly incompatible with water. One of the most useful and successfully marketed inorganic silicon compounds is silicon carbide.
Naturally occurring silicon is found in silicate and aluminosilicate minerals. One of the most common silicon compounds found in the Earth's crust is silicon dioxide or silica, which often occurs as quartz.
Organosilicon compounds are fairly stable due to the similarity in strength of the Si–C bond to the C–C bond. Organosilicates include silicone polymers.

Silicides

Many metal silicides are known, most of which have formulas that cannot be explained through simple appeals to valence: their bonding ranges from metallic to ionic and covalent. Some known stoichiometries are,,,,,,,,, MSi,,,, and. They are structurally more similar to the borides than the carbides, in keeping with the diagonal relationship between boron and silicon, although the larger size of silicon than boron means that exact structural analogies are few and far between. The heats of formation of the silicides are usually similar to those of the borides and carbides of the same elements, but they usually melt at lower temperatures. Silicides are known for all stable elements in groups 1–10, with the exception of beryllium: in particular, uranium and the transition metals of groups 4–10 show the widest range of stoichiometries. Except for copper, the metals in groups 11–15 do not form silicides. Instead, most form eutectic mixtures, although the heaviest stable ones – mercury, thallium, lead, and bismuth – are completely immiscible with liquid silicon.
Usually, silicides are prepared by direct reaction of the elements. For example, the alkali metals and alkaline earth metals react with silicon or silicon oxide to give silicides. Nevertheless, even with these highly electropositive elements true silicon anions are not obtainable, and most of these compounds are semiconductors. For example, the alkali metal silicides contain pyramidal tricoordinate silicon in the anion, isoelectronic with white phosphorus,. Metal-rich silicides tend to have isolated silicon atoms ; with increasing silicon content, catenation increases, resulting in isolated clusters of two or four silicon atoms at first, followed by chains, layers, or three-dimensional networks of silicon atoms spanning space as the silicon content rises even higher.
The silicides of the group 1 and 2 metals usually are more reactive than the transition metal silicides. The latter usually do not react with aqueous reagents, except for hydrofluoric acid; however, they do react with much more aggressive reagents such as liquid potassium hydroxide, or gaseous fluorine or chlorine when red-hot. The pre-transition metal silicides instead readily react with water and aqueous acids, usually producing hydrogen or silanes:
Products often vary with the stoichiometry of the silicide reactant. For example, is polar and non-conducting and has the anti- structure with single isolated silicon atoms, and reacts with water to produce calcium hydroxide, hydrated silicon dioxide, and hydrogen gas. CaSi with its zigzag chains of silicon atoms instead reacts to give silanes and polymeric, while with its puckered layers of silicon atoms does not react with water, but will react with dilute hydrochloric acid: the product is a yellow polymeric solid with stoichiometry.

Silanes

Speculation on silicon hydride chemistry started in the 1830s, contemporary with the development of synthetic organic chemistry. Silane itself, as well as trichlorosilane, were first synthesised by Friedrich Wöhler and Heinrich Buff in 1857 by reacting aluminium–silicon alloys with hydrochloric acid, and characterised as and by Charles Friedel and Albert Ladenburg in 1867. Disilane ) followed in 1902, when it was first made by Henri Moissan and Samuel Smiles by the protonolysis of magnesium silicides. Further investigation had to wait until 1916 because of the great reactivity and thermal instability of the silanes; it was then that Alfred Stock began to study silicon hydrides in earnest with new greaseless vacuum techniques, as they were found as contaminants of his focus, the boron hydrides. The names silanes and boranes are his, based on analogy with the alkanes. The Moissan and Smiles method of preparation of silanes and silane derivatives via protonolysis of metal silicides is still used, although the yield is lowered by the hydrolysis of the products that occurs simultaneously, so that the preferred route today is to treat substituted silanes with hydride reducing agents such as lithium aluminium hydride in etheric solutions at low temperatures. Direct reaction of HX or RX with silicon, possibly with a catalyst such as copper, is also a viable method of producing substituted silanes.
The silanes comprise a homologous series of silicon hydrides with a general formula of. They are all strong reducing agents. Unbranched and branched chains are known up to n=8, and the cycles and are also known. The first two, silane and disilane, are colourless gases; the heavier members of the series are volatile liquids. All silanes are very reactive and catch fire or explode spontaneously in air. They become less thermally stable with room temperature, so that only silane is indefinitely stable at room temperature, although disilane does not decompose very quickly. They decompose to form polymeric polysilicon hydride and hydrogen gas. As expected from the difference in atomic weight, the silanes are less volatile than the corresponding alkanes and boranes, but more so than the corresponding germanes. They are much more reactive than the corresponding alkanes, because of the larger radius of silicon compared to carbon facilitating nucleophilic attack at the silicon, the greater polarity of the Si–H bond compared to the C–H bond, and the ability of silicon to expand its octet and hence form adducts and lower the reaction's activation energy.
Silane pyrolysis gives polymeric species and finally elemental silicon and hydrogen; indeed ultrapure silicon is commercially produced by the pyrolysis of silane. While the thermal decomposition of alkanes starts by the breaking of a C–H or C–C bond and the formation of radical intermediates, polysilanes decompose by eliminating silylenes : or :SiHR, as the activation energy of this process is much less than the Si–Si and Si–H bond energies. While pure silanes do not react with pure water or dilute acids, traces of alkali catalyse immediate hydrolysis to hydrated silicon dioxide. If the reaction is carried out in methanol, controlled solvolysis results in the products,, and. The Si–H bond also adds to alkenes, a reaction which proceeds slowly and speeds up with increasing substitution of the silane involved. At 450 °C, silane participates in an addition reaction with acetone, as well as a ring-opening reaction with ethylene oxide. Direct reaction of the silanes with chlorine or bromine results in explosions at room temperature, but the reaction of silane with bromine at −80 °C is controlled and yields bromosilane and dibromosilane. The monohalosilanes may be formed by reacting silane with the appropriate hydrogen halide with an catalyst, or by reacting silane with a solid silver halide in a heated flow reactor:
Among the derivatives of silane, iodosilane and potassium silanide are very useful synthetic intermediates in the production of more complicated silicon-containing compounds: the latter is a colourless crystalline ionic solid containing K⁺ cations and anions in the NaCl structure, and is made by the reduction of silane by potassium metal. Additionally, the reactive hypervalent species is also known. With suitable organic substituents it is possible to produce stable polysilanes: they have surprisingly high electric conductivities, arising from sigma delocalisation of the electrons in the chain.

Halides

Silicon and silicon carbide readily react with all four stable halogens, forming the colourless, reactive, and volatile silicon tetrahalides. Silicon tetrafluoride also may be made by fluorinating the other silicon halides, and is produced by the attack of hydrofluoric acid on glass. Heating two different tetrahalides together also produces a random mixture of mixed halides, which may also be produced by halogen exchange reactions. The melting and boiling points of these species usually rise with increasing atomic weight, though there are many exceptions: for example, the melting and boiling points drop as one passes from through to. The shift from the hypoelectronic elements in Group 13 and earlier to the Group 14 elements is illustrated by the change from an infinite ionic structure in aluminium fluoride to a lattice of simple covalent silicon tetrafluoride molecules, as dictated by the lower electronegativity of aluminium than silicon, the stoichiometry, and the smaller size of the silicon atom compared to the aluminium atom.
Silicon tetrachloride is manufactured on a huge scale as a precursor to the production of pure silicon, silicon dioxide, and some silicon esters. The silicon tetrahalides hydrolyse readily in water, unlike the carbon tetrahalides, again because of the larger size of the silicon atom rendering it more open to nucleophilic attack and the ability of the silicon atom to expand its octet which carbon lacks. The reaction of silicon tetrafluoride with excess hydrofluoric acid produces the octahedral hexafluorosilicate anion.
Analogous to the silanes, halopolysilanes also are known. While catenation in carbon compounds is maximised in the hydrogen compounds rather than the halides, the opposite is true for silicon, so that the halopolysilanes are known up to at least,, and. A suggested explanation for this phenomenon is the compensation for the electron loss of silicon to the more electronegative halogen atoms by pi backbonding from the filled p_π orbitals on the halogen atoms to the empty d_π orbitals on silicon: this is similar to the situation of carbon monoxide in metal carbonyl complexes and explains their stability. These halopolysilanes may be produced by comproportionation of silicon tetrahalides with elemental silicon, or by condensation of lighter halopolysilanes.