o-, m-, and p-Carboranes and Their Anions: Ab Initio Calculations of Structures, Electron Affinities, and Acidities.
Ab initio geometry optimizations have been performed for o-, m-, and p-C(2)B(10)H(12) carborane cages and their mono- and dianions at the Hartree-Fock 3-21G, 6-31G, and 6-31G levels. The para-compound is the most stable with a calculated DeltaH(para-meta) value of -10 kJ/mol and a calculated DeltaG(975K)(para-meta) value of -3 kJ/mol. These small calculated energy differences disagree with the experimental heats of formation, which suggest DeltaH to be ca. -65 kJ/mol, but they agree with equilibrium gas mixture measurements at 975 K, which suggest a DeltaG value of ca. -1 kJ/mol. Electron distributions, electron affinities, and acidic properties of the carboranes are presented. The structures of the mono- and dianions were determined by optimization, starting from the three neutral carborane cages; we find three energy minima for the C(2)B(10)H(12)(2)(-) ion. The lowest-energy dianion is a nido-structure topped by a six-membered ring with the two C atoms in the meta position. The captured electrons become distributed over all the H atoms.
Hermansson
Kersti
K
Inorganic Chemistry, The Ångström Laboratory, Uppsala University, Box 538, S-75121 Uppsala, Sweden, and Organic Chemistry, Uppsala University, Box 531, S-75121 Uppsala, Sweden.
Wójcik
Mark
M
Sjöberg
Stefan
S