Functionalized nanodiamonds part I. An experimental assessment of diamantane and computational predictions for higher diamondoids.
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 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-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.
Fokin
Andrey A
AA
Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev, Ukraine.
Tkachenko
Boryslav A
BA
Gunchenko
Pavel A
PA
Gusev
Dmitriy V
DV
Schreiner
Peter R
PR