(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, or
(2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl or
TEMPO is a
chemical compound with the formula (CH
2)
3(CMe
2)
2NO. This
heterocyclic compound is a red-orange, sublimable solid. As a stable
radical, it has applications in chemistry and biochemistry. TEMPO was discovered by Lebedev and Kazarnowskii in 1960. It is prepared by oxidation of
2,2,6,6-tetramethylpiperidine. TEMPO is widely used as a radical marker, as a structural probe for biological systems in conjunction with
electron spin resonance spectroscopy, as a reagent in
organic synthesis, and as a mediator in controlled
radical polymerization. The stability of this radical is attributed to the resonance provided by non-bonding electrons on the nitrogen atom, which form a 2c3e (half-) bond between nitrogen and oxygen, and
hyperconjugative ability. Additional stability arises from the steric protection provided by the four
methyl groups adjacent to the nitroxyl group; however, the methyl groups prevent a double bond occurring between either carbon adjacent to nitrogen. The stability of the radical is also indicated by the weakness of the O-H bond in the hydrogenated derivative TEMPO-H. With an O-H
bond dissociation energy of about 70 kcal/mol, this bond is about 30% weaker than a typical O-H bond.