Journal article

Publication year: 2005

Pages: 7091-7101

Journal: Chemistry - A European Journal

Volume number: 11

Issue number: 23

ISSN: 0947-6539

DOI Link: https://doi.org/10.1002/chem.200500031

Publisher: Wiley

Abstract: 
The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T-d-pentamantane 6, and D-3d-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol-1 for 7). The reactivity of I was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C-center dot (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyidioxirane, m-chloroperbenzoic acid, and CrO2Cl2) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br-2, 100% HNO3), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents.

Harvard Citation style: Fokin, A., Tkachenko, B., Gunchenko, P., Gusev, D. and Schreiner, P. (2005) Functionalized nanodiamonds, Part I: An experimental assessment of diamantane and computational predictions for higher diamondoids, Chemistry - A European Journal, 11(23), pp. 7091-7101. https://doi.org/10.1002/chem.200500031

APA Citation style: Fokin, A., Tkachenko, B., Gunchenko, P., Gusev, D., & Schreiner, P. (2005). Functionalized nanodiamonds, Part I: An experimental assessment of diamantane and computational predictions for higher diamondoids. Chemistry - A European Journal. 11(23), 7091-7101. https://doi.org/10.1002/chem.200500031