A trimethylsilyl group (abbreviated TMS) is a

functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...

organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

. This group consists of three

methyl In organic chemistry, a methyl group is an alkyl derived from methane, containing one carbon atom bonded to three hydrogen atoms, having chemical formula (whereas normal methane has the formula ). In formulas, the group is often abbreviated as ...

groups bonded to a

silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...

atom minus;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 The van der Waals surface of a molecule is an abstract representation or model of that molecule, illustrating where, in very rough terms, a surface might reside for the molecule based on the hard cutoffs of van der Waals radii for individual a ...

, which makes it useful in a number of applications. A trimethylsilyl group bonded to a methyl group forms

tetramethylsilane Tetramethylsilane (abbreviated as TMS) is the organosilicon compound with the formula Si(CH3)4. It is the simplest tetraorganosilane. Like all silanes, the TMS framework is tetrahedral. TMS is a building block in organometallic chemistry but als ...

, which is abbreviated as TMS as well. Compounds with trimethylsilyl groups are not normally found in nature. Chemists sometimes use a trimethylsilylating

reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...

to derivatize rather non-volatile compounds such as certain

alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...

phenols In organic chemistry, phenols, sometimes called phenolics, are a class of chemical compounds consisting of one or more hydroxyl groups (− O H) bonded directly to an aromatic hydrocarbon group. The simplest is phenol, . Phenolic compounds ar ...

, or

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...

s by substituting a trimethylsilyl group for a hydrogen in the

hydroxyl group In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...

s on the compounds. This way trimethylsiloxy groups minus;O-Si(CH₃)₃are formed on the molecule. A couple of examples of trimethylsilylating agents include

trimethylsilyl chloride Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound ( silyl halide), with the formula , often abbreviated or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely u ...

and

bis(trimethylsilyl)acetamide Bis(trimethylsilyl)acetamide (BSA) is an organosilicon compound with the formula (Me = CH3). It is a colorless liquid that is soluble in diverse organic solvents, but reacts rapidly with moisture and solvents containing OH and NH groups. It i ...

. Trimethylsilyl groups on a molecule have a tendency to make it more volatile, often making the compounds more amenable to analysis by

gas chromatography Gas chromatography (GC) is a common type of chromatography used in analytical chemistry for Separation process, separating and analyzing compounds that can be vaporized without Chemical decomposition, decomposition. Typical uses of GC include t ...

mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is used ...

. An example of such trimethylsilylation is mentioned in the

Brassicasterol Brassicasterol (24-methyl cholest-5,22-dien-3β-ol) is a 28-carbon sterol synthesised by several unicellular algae (phytoplankton) and some terrestrial plants, like rape. This compound has frequently been used as a biomarker for the presence of ( ...

article. Such derivatizations are often done on a small scale in special

vial A vial (also known as a phial or flacon) is a small glass or plastic vessel or bottle, often used to store medication in the form of liquids, powders, or capsules. They can also be used as scientific sample vessels; for instance, in autosam ...

s. When attached to certain functional groups in a reactant molecule, trimethylsilyl groups may also be used as temporary

protecting group A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. It plays an important role in multistep organic synthesis. In man ...

s during

chemical synthesis Chemical synthesis (chemical combination) is the artificial execution of chemical reactions to obtain one or several products. This occurs by physical and chemical manipulations usually involving one or more reactions. In modern laboratory uses ...

or some other

chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...

s. In

chromatography In chemical analysis, chromatography is a laboratory technique for the Separation process, separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it ...

, derivitization of accessible

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 c ...

groups in a bonded stationary phase with trimethylsilyl groups is referred to as

endcapping In chromatography, endcapping refers to the replacement of accessible silanol groups in a bonded stationary phase by trimethylsilyl A trimethylsilyl group (abbreviated TMS) is a functional group in organic chemistry. This group consists of three ...

. In an

NMR spectrum Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique based on re-orientation of atomic nuclei with non-zero nuclear spins in an external magnetic fi ...

, signals from atoms in trimethylsilyl groups in compounds will commonly have chemical shifts close to the

reference peak at 0 ppm. Also compounds, such as high temperature silicone "

stopcock A stopcock is a form of valve used to control the flow of a liquid or gas. The term is not precise and is applied to many different types of valve. The only consistent attribute is that the valve is designed to completely stop the flow when clo ...

" grease, which have

polysiloxane In organosilicon and polymer chemistry, a silicone or polysiloxane is a polymer composed of repeating units of siloxane (, where R = organic group). They are typically colorless oils or rubber-like substances. Silicones are used in sealants ...

s (often called silicones) in them will commonly show peaks from their methyl groups (attached to the silicon atoms) having NMR chemical shifts close to the tetramethylsilane standard peak, such as at 0.07 ppm in CDCl₃. Otherwise very reactive molecules can be isolated when enveloped by bulky trimethylsilyl groups. This effect can be observed in

tetrahedrane Tetrahedrane is a hypothetical platonic hydrocarbon with chemical formula and a tetrahedral structure. The molecule would be subject to considerable angle strain and has not been synthesized . However, a number of derivatives have been prepa ...

Super silyl groups

Related to trimethylsilyl groups are "super" silyl groups of which there exist two varieties: A silicon group connected to three trimethylsilyl groups makes a tri(trimethylsilyl)silyl group (TTMSS or TMS₃Si) and a silicon group connected to three

tert-butyl In organic chemistry, butyl is a four-carbon alkyl radical or substituent group with general chemical formula , derived from either of the two isomers (''n''-butane and isobutane) of butane. The isomer ''n''-butane can connect in two ways, giv ...

groups. The TTMSS group was proposed in 1993 by Hans Bock. With a van der Waals volume of up to 7 cubic

angstrom The angstrom (; ) is a unit of length equal to m; that is, one ten-billionth of a metre, a hundred-millionth of a centimetre, 0.1 nanometre, or 100 picometres. The unit is named after the Swedish physicist Anders Jonas Ångström (1814–18 ...

it surpasses the related TIPS group (around 2) and one potential application is its use as a temporary substituent promoting

asymmetric induction Asymmetric induction describes the preferential formation in a chemical reaction of one enantiomer (enantioinduction) or diastereoisomer (diastereoinduction) over the other as a result of the influence of a chiral feature present in the substrate ...

for example in this

diastereoselective In stereochemistry, diastereomers (sometimes called diastereoisomers) are a type of stereoisomer. Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have dif ...

one-pot reaction In chemistry a one-pot synthesis is a strategy to improve the efficiency of a chemical reaction in which a reactant is subjected to successive chemical reactions in just one reactor. This is much desired by chemists because avoiding a lengthy ...

involving two sequential

Mukaiyama aldol reaction In organic chemistry, the Mukaiyama aldol addition is an organic reaction and a type of aldol reaction between a silyl enol ether () and an aldehyde () or formate (). The reaction was discovered by Teruaki Mukaiyama in 1973. His choice of reacta ...

s: :

TTMSS can also stand for tris(trimethylsilyl)silane, which is comparable as a chemical reagent to

tributyltin hydride Tributyltin hydride is an organotin compound with the formula (C4H9)3SnH. It is a colorless liquid that is soluble in organic solvents. The compound is used as a source of hydrogen atoms in organic synthesis. Synthesis and characterization The c ...

without the associated toxicity concern of

organotin Organotin chemistry is the scientific study of the synthesis and properties of organotin compounds or stannanes, which are organometallic compounds containing tin–carbon bonds. The first organotin compound was diethyltin diiodide (), discove ...

and

tributyltin Tributyltin (TBT) is an umbrella term for a class of organotin compounds which contain the group, with a prominent example being tributyltin oxide. For 40 years TBT was used as a biocide in anti-fouling paint, commonly known as bottom paint, ...

compounds. The reagent is employed in

radical reductions Radical (from Latin: ', root) may refer to: Politics and ideology Politics *Classical radicalism, the Radical Movement that began in late 18th century Britain and spread to continental Europe and Latin America in the 19th century *Radical politics ...

hydrosilylation Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds across unsaturated bonds."Hydrosilylation A Comprehensive Review on Recent Advances" B. Marciniec (ed.), Advances in Silicon Science, Springer Science, 200 ...

and

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