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Carborane Anions

My research interests center on the synthesis and computational studies of molecules containing icosahedral boron clusters, especially CB11H12- and its derivatives.The derivatization chemistry of these compounds is advancing, their applications are beginning to emerge,1,2 and there are a tremendous number of unexplored possibilities.



CB11H12- and some of its derivatives.

Weakly coordinating anions based on icosahedral carborane anions have been used in the preparation of stable carbocations, 3,4 a class of extremely strong solid Brønsted acids,5,6 and a powerful new methylating reagent.7 Improved anion properties relative to those of the parent CB11H12- anion have been achieved by attaching electron withdrawing and/or bulky substituents around the exterior of the cage. For the most part, efforts have focused on replacement of H-atom substituents on the cage with either halogens,8 or with alkyl9,10 and aryl8 groups and their fluorinated analogues11. Tailoring properties of the anion by modifying substituent patterns with other groups which may confer improved weakly-coordinating properties has yet to be explored. One major goal for this research is the preparation of new derivatives of CB11H12- and the evaluation of their performance as weakly-coordinating anions.

Advances in the synthetic modifications which can be made to the CB11H12- group can also be expected to improve its potential as a useful moiety in Boron Neutron Capture Therapy, where the development of CB11H12- based systems has lagged that of the icosahedral dicarbaboranes, (e.g. ortho-, meta-, and para-C2B10H12).

References

  1. Grimes, Russel N., "Boron Clusters Come of Age," Journal of Chemical Education, 2004, 5, 658-672.

  2. Reed, C. A., "Carborane Acids. New "Strong Yet Gentle'' Acids For Organic and Inorganic Chemistry," Chemical Communications, 2005, , 1669-1677.

  3. Müller T., Juhasz, M., Reed, C. A., "The X-Ray Structure of a Vinyl Cation," Angewandte Chemie International Edition, 2004, 43, 1543-1546.

  4. Kato, T., Reed, C. A., "Putting t-Butyl Cation in a Bottle," Angewandte Chemie International Edition, 2004, 43, 2908-2911.

  5. Juhasz, M., Hoffmann, S., Stoyanov, E., Kim, K-C., Reed, C. A., "The Strongest Isolable Acid," Angewandte Chemie International Edition, 2004, 40, 5352-5355.

  6. Stoyanov, E. S., Hoffmann, S. P., Juhasz, M., Reed, C. A., "The Structure of the Strongest Brønsted Acid: The Carborane Acid H(CHB11Cl11)," Journal of the American Chemical Society, 2006, , 3160-3161.

  7. Kato, T., Stoyanov, E., Geier, J., Grutzmacher, H., Reed, C. A., "Alkylating Agents Stronger than Alkyl Triflates," Journal of the American Chemical Society, 2004, 126, 12451-12457.

  8. Jelinek, T., Baldwin, P., Scheidt, W. R., Reed, C. A., "New Weakly Coordinating Anions. 2. Derivatization of the Carborane Anion CB11H12-," Inorganic Chemistry, 1993, 32, 1982-1990.

  9. King, B., Janousek, Z., Grüner, B., Trammell, M., Noll, B. C., Michl, J., "Dodecamethylcarba-closo-dodecaborate(-) Anion, CB11Me12-," Journal of the American Chemical Society, 1996, 118, 3313-3314.

  10. Stasko, D., Reed, C. A., "Optimizing the Least Nucleophilic Anion," Journal of the American Chemical Society, 2002, 124, 1148-1149.

  11. King, B. T., Michl, J., "The Explosive "Inert" Anion CB11(CF3)12-," Journal of the American Chemical Society, 2000, 122, 10255-10256.

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