20.9
Reactividad radical: efectos estéricos
La presencia de grupos donadores, atractores o conjugadores de electrones adyacentes a un centro radical imparte estabilización electrónica a los radi…
Recordemos que la presencia de grupos donantes de electrones, salientes de electrones y conjugantes adyacentes a un centro radical da como resultado radicales estabilizados electrónicamente.
Algunos de estos radicales estabilizados electrónicamente se conocen como radicales persistentes. Estos radicales son notablemente estables; Algunos incluso pueden ser aislados y purificados.
Además de los factores electrónicos, los factores estéricos también contribuyen a la estabilidad de estos radicales persistentes.
Por ejemplo, considere el radical trifenilmetilo. La estabilidad excepcionalmente alta de este radical se debe a la presencia de tres anillos de fenilo.
Los tres anillos circundantes se tuercen 30° fuera del avión en una conformación similar a la de una hélice.
Como resultado, el carbono central que lleva el carácter radical está protegido estéricamente por los anillos de fenilo retorcidos, lo que hace que el radical sea altamente estable e indisponible para las reacciones.
En general, los efectos estéricos hacen que un radical sea más estable y menos reactivo.
View the full transcript and gain access to JoVE Core videos
Q1: What role do steric effects play in radical stability?
Steric effects significantly enhance radical stability by shielding the radical center from molecular attack. Bulky groups surrounding the radical site create steric hindrance, making the radical less accessible and therefore less reactive. This protection reduces the likelihood of unwanted side reactions and contributes to the formation of persistent radicals that can be isolated and purified.
Q2: How does the triphenylmethyl radical demonstrate steric stabilization?
The triphenylmethyl radical achieves exceptional stability through three phenyl rings twisted 30° out of plane in a propeller conformation. These twisted rings sterically shield the central carbon bearing the radical character, making it highly unavailable for reactions. This steric protection is the primary reason for the triphenylmethyl radical's remarkable stability and persistence.
Q3: What are persistent radicals and how do they form?
Persistent radicals are remarkably stable radicals that result from combined electronic and steric stabilization. Electronic stabilization comes from electron-donating, electron-withdrawing, or conjugating groups adjacent to the radical center. Examples include triphenylmethyl, tetramethylpiperidine-N-oxide, and 2,2-diphenyl-1-picrylhydrazyl radicals, which can be isolated and purified due to their exceptional stability.
Q4: Why does steric shielding decrease radical reactivity?
Steric shielding decreases radical reactivity by physically blocking access to the radical center. When bulky groups surround the radical site, they prevent other molecules from approaching and reacting with it. This reduced accessibility makes sterically hindered radicals less likely to participate in radical substitution or addition reactions, effectively stabilizing them against further transformation.
Q5: How do electronic factors contribute to persistent radical stability?
Electronic factors stabilize radicals through electron-donating groups that increase electron density at the radical center, electron-withdrawing groups that delocalize radical character, or conjugating groups that spread unpaired electron density across multiple atoms. These electronic effects work alongside steric factors to create persistent radicals with exceptional stability and reduced reactivity.
Q6: What is the propeller conformation in the triphenylmethyl radical?
The propeller conformation describes the three-dimensional arrangement where the three phenyl rings of the triphenylmethyl radical twist 30° out of the molecular plane. This twisted geometry resembles a propeller and positions the phenyl rings to maximally shield the central carbon atom. The propeller arrangement is crucial for the radical's exceptional stability and resistance to further reactions.
Q7: How do steric and electronic factors work together in radical stabilization?
Steric and electronic factors combine synergistically to create highly stable persistent radicals. Electronic factors stabilize the radical through conjugation and group effects, while steric factors provide physical protection by shielding the radical center from molecular attack. Together, these factors reduce radical reactivity and enable isolation and purification of certain radicals for study using electron paramagnetic resonance epr spectroscopy.