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The Adamantaneland Revisited.
Pedro H Antunes Silva1, Amir L Perlin1, Cleverson J F de Oliveira2
1Instituto de Química, Universidade Federal do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, CT A-622, Cid. Univ., Rio de Janeiro, RJ 21941-909, Brazil.
Diamondoids, like adamantane, are stable petroleum components. This study reveals that while adamantane is stable, its carbocation is not the most stable, suggesting a link between 1-methylhexahydroindene and diamondoid formation.
Area of Science:
- Geochemistry
- Organic Chemistry
- Petroleum Science
Background:
- Diamondoids are stable, cage-like hydrocarbons found in petroleum.
- Their geological stability makes them valuable markers, but formation pathways are poorly understood.
- Limited knowledge hinders broader applications compared to conventional biomarkers.
Purpose of the Study:
- To investigate the formation pathways of adamantane, the simplest diamondoid.
- To explore carbocationic mechanisms originating from isomeric hydrocarbons.
- To assess the thermodynamic stability of adamantane and its carbocation relative to isomers.
Main Methods:
- Computational chemistry using the M06-2X/cc-pVTZ level of theory.
- Assessed thermodynamic stability of adamantane (C10H16) and 1-adamantyl cation (C10H15+) isomers.
- Compared stability of adamantane isomers and 1-adamantyl cation isomers.
Main Results:
- Adamantane is confirmed as the most stable C10H16 isomer.
- The 1-adamantyl cation is not the most stable C10H15+ species.
- The most stable carbocations are allylic species with the 1-methylhexahydroindene ring system.
Conclusions:
- Hydrocarbons with the 1-methylhexahydroindene structure may be geochemically linked to diamondoid formation.
- Ratios of these hydrocarbons could be significant geochemical indicators.
- Understanding these pathways enhances the application of diamondoids as geological markers.
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