8.6
Effetti dell'elettrone π sullo Shift Chimico: composti aromatici e antiaromatici
Nei composti aromatici, come il benzene, la circolazione di (4n + 2) elettroni π crea una corrente ad anello diamagnetica o diatropica attorno al peri…
Nei composti aromatici, la circolazione di (4n + 2) elettroni π crea una corrente ad anello diamagnetica o diatropica attorno ai loro perimetri.
Questa corrente induce un campo magnetico che si oppone al campo esterno all'interno dell'anello e lo rinforza all'esterno.
Quindi, i protoni nel benzene sono deschermati e mostrano elevati spostamenti chimici da 6,5 a 8,5 ppm.
L'effetto schermante al centro degli anelli aromatici è evidente in molecole complesse, come gli annuleni.
Nel [18]annulene, i protoni al di fuori dell'anello sono deschermati e risuonano a δ 9,3, mentre quelli al centro risuonano intorno a δ −3,0, al di sotto della TMS.
Nei composti anti-aromatici con 4n π-elettroni, la corrente dell'anello è paratropica e scorre nella direzione opposta a quella osservata nei composti aromatici.
Il conseguente cambiamento nella direzione del campo indotto protegge i protoni all'esterno dell'anello e descudia quelli all'interno, come si vede nel [16]annulene.
View the full transcript and gain access to JoVE Core videos
Q1: What is a diatropic ring current and how does it affect proton chemical shifts in aromatic compounds?
In aromatic compounds, circulation of (4n + 2) π-electrons creates a diamagnetic or diatropic ring current around the molecule's perimeter. This current induces a magnetic field that opposes the external field inside the ring and reinforces it outside. Consequently, aromatic protons are deshielded and exhibit high chemical shifts, typically 6.5–8.5 ppm in benzene.
Q2: Why do protons at the center of annulenes resonate at unusually high or low chemical shift values?
The shielding effect at the center of aromatic rings is dramatic in annulenes. In [18]annulene, external protons are deshielded and resonate at δ 9.3, while central protons are so strongly shielded they resonate at δ −3.0, below TMS. This extreme upfield shift reflects the intense diamagnetic shielding from the diatropic ring current.
Q3: How does the ring current in antiaromatic compounds differ from that in aromatic compounds?
Antiaromatic compounds with 4n π-electrons generate a paratropic ring current flowing opposite to the diatropic current in aromatic systems. This reversal changes the induced magnetic field direction, shielding protons outside the ring and deshielding those inside, as observed in [16]annulene.
Q4: What chemical shift values are observed for external and internal protons in [16]annulene?
In [16]annulene, an antiaromatic compound, the paratropic ring current produces opposite shielding effects compared to aromatic systems. External protons are shielded and resonate upfield, while internal protons are deshielded and resonate downfield, demonstrating how the 4n π-electron system fundamentally alters magnetic field interactions.
Q5: How can NMR spectroscopy distinguish between aromatic and antiaromatic ring systems?
Aromatic compounds show characteristic deshielded external protons at 6.5–8.5 ppm due to diatropic ring currents, while antiaromatic compounds display opposite shielding patterns with external protons shifted upfield. These contrasting chemical shift patterns directly reflect the opposing directions of ring currents generated by (4n + 2) versus 4n π-electron systems.
Q6: What role does the (4n + 2) rule play in determining aromatic ring current behavior?
The (4n + 2) π-electron rule governs aromatic stability and ring current direction. Compounds following this rule generate diatropic currents that deshield external protons and shield internal protons. Deviations from this rule, such as 4n systems, produce paratropic currents with reversed shielding effects, fundamentally altering NMR chemical shift patterns.
Q7: Why are annulenes useful models for studying ring current effects on chemical shifts?
Annulenes are ideal for studying ring current effects because they contain protons both outside and inside the ring system, allowing direct comparison of shielding and deshielding effects. Their well-defined π-electron counts and symmetric structures make them excellent examples of how diatropic and paratropic ring currents produce dramatically different chemical shift values.