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Catalytic epoxidation of C60 using Mo(O)2(acac)2/(t)BuOOH
Robin E Anderson1, Andrew R Barron
1Department of Chemistry, Rice University, Houston, TX 77005, USA.
Dalton Transactions (Cambridge, England : 2003)
|November 30, 2012
Summary
Researchers synthesized highly oxygenated fullerenes, C60On, using a molybdenum catalyst and tert-butyl hydroperoxide. Reaction conditions controlled oxygenation levels and revealed cage-opened fullerene derivatives under mass spectrometry analysis.
Area of Science:
- Fullerene Chemistry
- Organic Synthesis
- Catalysis
Background:
- Fullerenes (C60) are carbon allotropes with unique electronic and structural properties.
- Controlled oxidation of fullerenes is crucial for tuning their properties for various applications.
- Understanding fullerene oxidation pathways is essential for developing new synthetic methodologies.
Purpose of the Study:
- To synthesize highly oxygenated fullerenes (C60On, 1 ≤ n ≤ 13) using a specific catalytic system.
- To investigate the influence of reaction parameters (catalyst ratio, temperature, oxidant concentration) on fullerene oxygenation.
- To characterize the resulting oxygenated fullerenes and identify any cage-opened byproducts.
Main Methods:
- Catalytic oxidation of C60 using molybdenum(II) bis(acetylacetonate) (Mo(O)2(acac)2) and tert-butyl hydroperoxide ((t)BuOOH).
- Systematic variation of catalyst to C60 ratio, reaction temperature, and (t)BuOOH concentration.
- Analysis of reaction products using MALDI mass spectrometry to determine oxygenation levels and identify cage-opened species.
Main Results:
- Successfully synthesized highly oxygenated fullerenes C60On (1 ≤ n ≤ 13).
- Yield and oxygenation degree were modulated by catalyst:C60 ratio and temperature (higher values favored higher oxygenation).
- Increased (t)BuOOH concentration shifted product distribution towards lower oxygenation.
- MALDI-MS revealed cage-opened products (Cx, x=54, 56, 58) and their oxygenated derivatives (CxOn) for highly oxygenated samples.
Conclusions:
- The Mo(O)2(acac)2 catalyzed oxidation provides a tunable route to highly oxygenated fullerenes.
- Reaction parameters significantly influence the extent of fullerene oxygenation and product distribution.
- The formation of cage-opened fullerene derivatives under MS conditions highlights the structural lability of highly oxygenated fullerenes.
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