Silanol

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.Vadapalli Chandrasekhar, Ramamoorthy Boomishankar, Selvarajan Nagendran: Recent Developments in the Synthesis and Structure of Organosilanols. Chem. Rev. 2004, volume 104, pp 5847–5910. If a silanol contains one or more organic residues, it is an organosilanol.

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Preparation

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From alkoxysilanes The first isolated example of a silanol was , reported in 1871 by Albert Ladenburg. He prepared the “silicol” by hydrolysis of (Et = ethyl group).A. Ladenburg: On the silicoheptyl series, from Deut. Chem. Ges. Ber., iv, 901 as summarized in "Organic chemistry" J. Chem. Soc., 1872, vol. 25, pp. 133–156.

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From silyl halides and related compounds Silanols are generally synthesized by hydrolysis of halosilanes, alkoxysilanes, or aminosilanes. Chlorosilanes are the most common reactants:

R₃Si–Cl + H₂O → R₃Si–OH + HCl

The hydrolysis of fluorosilanes requires more forcing reagents, i.e. alkali. The alkoxysilanes () of the type are slow to hydrolyze. Compared to the silyl ethers, silyl acetates are faster to hydrolyze, with the advantage that the released acetic acid is less aggressive. For this reason silyl acetates are sometimes recommended for applications.

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By oxidation of silyl hydrides An alternative route involves oxidation of hydrosilanes. A wide range of oxidants have been employed including air, , , and potassium permanganate (for hindered silanes). In the presence of metal catalysts, silanes undergo hydrolysis:

R₃Si–H + H₂O → R₃Si–OH + H₂

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Structure and examples

The Si–O bond distance is typically about 1.65 Angstrom.Paul D. Lickiss: The Synthesis and Structure of Organosilanols, Advances in Inorganic Chemistry Volume 42, 1995, Pages 147–262 In the solid state, silanols engage in hydrogen-bonding.Beckmann, J.; Dakternieks, D.; Duthie, A.; Larchin, M. L.; Tiekink, E. R. T.: Tert-butoxysilanols as model compounds for labile key intermediates of the sol-gel process: crystal and molecular structures of (t-BuO)₃SiOH and HO(t-BuO)₂SiO₂H, Appl. Organomet. Chem. 2003, 17, 52–62.

Most silanols have only one OH group, e.g. trimethylsilanol. Also known are some silanediols, e.g., diphenylsilanediol. For sterically bulky substituents, even silanetriols have been prepared.R. Pietschnig and S. Spirk: The Chemistry of Organo Silanetriols. Coord. Chem. Rev. 2016, 87-106.

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Reactions

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Acidity

Silanols are more acidic than the corresponding alcohols. This trend contrasts with the fact that Si is far less electronegative than carbon (1.90 vs 2.55, respectively). For Et₃SiOH, the p K_a is estimated at 13.6 vs. 19 for tert-butyl alcohol. The p K_a of is 11. Because of their greater acidity, silanols can be fully deprotonated in aqueous solution, especially the arylsilanols. The conjugate base is called a siloxide or a silanolate.

Despite the disparity in acidity, the basicities of alkoxides and siloxides are similar.

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Condensation and the sol-gel process

Silanols condense to give siloxane:

The conversions of silyl halides, acetates, and ethers to siloxanes proceed via silanols. The sol-gel process, which entails the conversion of, for example, into hydrated , proceeds via silanol intermediates.

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Occurrence

Silanols exist not only as chemical compounds, but are pervasive on the surface of silica and related . Their presence is responsible for the absorption properties of silica gel.Nawrocki, Jacek: The silanol group and its role in liquid chromatography, Journal of Chromatography A 1997, volume 779, 29–72. In chromatography, derivatization of accessible silanol groups in a bonded stationary phase with trimethylsilyl groups is referred to as endcapping. Organosilanols occur as intermediates in industrial processes such as the manufacturing of . Moreover, organosilanols occur as in the biodegradation of small ring in mammals.

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Biorelevance

Some silanediols and silanetriols inhibit hydrolytic enzymes such as thermolysinScott Sieburth, T. Nittoli, A. M. Mutahi and L. Guo: Silanediols: a new class of potent protease inhibitors, Angew. Chem. Int. Ed. 1998, volume 37, 812-814. and acetylcholinesterase.M. Blunder, N. Hurkes, M. List, S. Spirk and R. Pietschnig: Silanetriols as in vitro AChE Inhibitors, Bioorg. Med. Chem. Lett. 2011, volume 21, 363-365.

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Parent silanols

Literally, silanol refers to a single compound with the formula (Chemical Abstracts number 14475-38-8). The family ( n = 1, 2, 3, 4) are highly unstable and are mainly of interest to theoretical chemists. The perhydroxylated silanol, sometimes called orthosilicic acid, is often discussed in vague terms, but has not been well characterized.

• EL Salmawy, M.S., Nakahiro, Y., and Wakamatsu, T. (1993). The role of silanol group in flotation separation of quartz from feldspar using non-ionic surfactants, 18th IMPC, pp. 845–849, The Australian Institute of Mining and Metallurgical Engineering, Sydney, Australia.

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