Trimethylsilyl

:"For tetramethylsilane which also abbreviated as TMS see tetramethylsilane."

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 them useful in a number of applications.

A trimethylsilyl group bonded to a methyl group forms tetramethylsilane, which is abbreviated as TMS as well.

Compounds with trimethylsilyl groups are not normally found in nature. Chemists sometimes use a trimethylsilylating reagent to derivatize rather non-volatile compounds such as certain alcohols, phenols, or carboxylic acids by substituting a trimethylsilyl group for a hydrogen in the hydroxyl groups on the compounds. This way trimethylsiloxy groups are formed on the molecule. Trimethylsilyl groups on a molecule have a tendency to make it more volatile, often making the compounds more amenable to analysis by gas chromatography or mass spectrometry. Such derivatizations are often done on a small scale in special vials.

When attached to certain functional groups in a reactant molecule, trimethylsilyl groups may also be used as temporary protecting groups during chemical synthesis or some other chemical reactions.

In an NMR spectrum, signals from atoms in trimethylsilyl groups in compounds will commonly have chemical shifts close to the tetramethylsilane reference peak at 0 ppm. Also compounds, such as high temperature silicone "stopcock" grease, which have polysiloxanes (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. [Gottlieb, H. E.; Kotlyar, V.; Nudelman, A. "NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities". J. Org. Chem. 1997, 62("21"), pp 7512-7515. doi|10.1021/jo971176v]

Otherwise very reactive molecules can be isolated when enveloped by bulky trimethylsilyl groups. This effect can be observed in tetrahedranes.

uper silyl groups

] :

:

ee also

* Trimethylsilanol
* Tetramethylsilane

References