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Theoretical and Experimental Investigations of Fullerene Derivatives: C60H2, C60H4, C70H2, AND C60(CH2)2

Published online by Cambridge University Press:  22 February 2011

S. Joshua Jacobs ,
Kenneth T. Gillen ,
Paul A. Cahill ,
Craig C. Henderson  and
Celeste M. Rohlfing
S. Joshua Jacobs
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185-0368
Kenneth T. Gillen
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185-0368
Paul A. Cahill
Affiliation:
Sandia National Laboratories, Livermore, CA 94551
Craig C. Henderson
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185-0368
Celeste M. Rohlfing
Affiliation:
Sandia National Laboratories, Albuquerque, NM 87185-0368
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Abstract

Hydroboration of C70 in toluene yields a 2:1 mixture of 1,9-C70H2 and 7,8-C70H2. Equilibration of these two isomers in the presence of a Pt catalyst reveals a free energy difference of 1.4 ± 0.2 kcal/mol. Whereas semiempirical calculations have been found to predict the energy ordering of many fullerene derivatives incorrectly, ab initio Hartree-Fock (HF) calculations have been found to yield quantitative predictions of experiment. The HF/6-31G* level energy separation of l,9-C70H2 and 7,8-C70H2 of 1.3 kcal/mol is in excellent agreement with experiment. Relative stabilities of isomers of bis(methano)fullerenes were found to parallel those of analogous C60H4 isomers. Density functional theory (DFT) methods have been tested and are equivalent in accuracy to HF methods if similar basis sets are used. C60H2 and C60H4 can be efficiently produced on larger (≥ 50 mg) scales with diimide generated from potassium azodicarboxylate and acetic acid in o-dichlorobenzene.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 349: Symposium T – Novel Forms of Carbon II , 1994 , 145
Copyright
Copyright © Materials Research Society 1994

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References

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