Essential Factors for Controlling the Equilibrium in Reversible Rearrangement of M3N@Ih-C80 Fulleropyrrolidines: Exohedral Functional Groups versus Endohedral Metal Clusters
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2014-10
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Journal Article
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Abstract
The effects of exohedral moieties and endohedral metal clusters on the isomerization of M₃N@Iₕ‐C₈₀ products from the Prato reaction through [1,5]‐sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C₈₀ was the single essential factor in determining the equilibrium between the [6,6]‐isomer (kinetic product) and the [5,6]‐isomer. In all the derivatives, the [6,6]‐ and [5,6]‐Prato adducts with larger metal clusters, such as Y₃N and Gd₃N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal‐cluster size. Further DFT calculations and ¹³C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]‐ and [5,6]‐fulleropyrrolidines.
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published
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20 (43)
Pages / Article No.
14032 - 14039
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Wiley-VCH
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Subject
DFT calculations; Fullerenes; Isomerization; Nitrogen heterocycles; Prato reaction
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08687 - Gruppe Yamakoshi
Notes
Received 29 May 2014, Published online 5 September 2014.