Hückelovo pravidlo
Aby byla daná latka aromatická, musí být molekula planární, monocyklická, mít dokonale konjugovaný systém vazeb a splňovat právě onu Hückelovu podmínku. Ta říká, že počet pí-elektronů ve sloučenině musí být roven číslu 4n+2, tedy matematicky P= 4n+2, kde P je počet pí-elektronů a n je libovolné celé nezáporné číslo.
Ovšem proč zrovna 4n+2??? Co je na této kombinaci tak speciálního? Proč tedy zrovna 2, 6, 10, 14... pí-elektronů vede k aromaticitě a poměrně vysoké stabilitě, zatímco ostatní kombinace vedou k větší či menší nestabilitě. Odpověď se skrývá v "tajemné" teorii molekulových orbitalů (MO).
Pokud se totiž spočítají energetické hladiny molekulových orbitalů pro cyklické konjugované molekuly, ukáže se, že vždy existuje jeden nejníže ležící MO, nad kterým existují MO v degenerovaných párech. Tedy, při zaplňováníí MO je vždy potřeba dvou elektronů na zaplnění nejníže ležícího osamoceného MO a poté vždy čtyř elektronů na zaplnění každé z n následujících energetických hladin - dohromady tedy 2 + 4n. Každý jiný počet zanechá energetickou hladinu částečně nezaplněnou a tedy méně stabilní.
OBR: Molekulové orbitaly pro benzen:
1. Šipka vlevo ukazuje růst energie systému
2. Šest nedegenerovaných 2p atomových orbitalů (AO) šesti atomů uhlíku v cyklu benzenu s jedním elektronem v každém z nich
3. Při konjugaci a vzniku molekulových orbitalů vznikají tři vazebné MO o nižší energii než měly puvodní AO (dva jsou degenerované) a tři protivazebné MO o vyšší energii než měly původní AO (dva jsou opět degenerované)
4. Vazebné MO jsou zaplněny elektrony - je vidět, proč jich musí být právě 4n + 2 - tak dojde k zaplnění všech vazebných MO, kdyby jich byl jiný počet, některá místa by byla zbytečně volná.
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(Egorsek, 4. 5. 2023 8:31)
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(BruceKit, 10. 7. 2023 1:53)