H. Bock, R. Claridge, Camelia L. Bogdan
Jun 13, 2001
Citations
0
Influential Citations
4
Citations
Journal
Helvetica Chimica Acta
Abstract
Redox Reactions of Hexahydropyrene: Crystal Structures of Its Radical-Anion Salts as well as of Trihydropyrenylium Tetrachloroaluminate and Density-Functional-Theory Calculations Hexahydropyrene 1, a doubly propane-1,3-diyl-bridged peri-naphthalene derivative wtih 10 π-electrons allows both oxidation to its cation as well as reduction to its radical-anion salts, which could be crystallized and structurally characterized – a rather rare case for small unsaturated hydrocarbons. The unexpected formally threefold dehydrogenation by the oxidizing system AlCl3/H2CCl2 (Bock's reagent) generated the hitherto unknown 1,2,3-trihydropyrene cation in two polymorphic crystals, which contain 12 π-electrons delocalized over three anellated six-membered rings comprising 13 π-centers. Structural comparison of the altogether four crystallized redox products [K+solv][M.−] 2a, [K+solv][M.−]∞2b, [Na+solv][M.−] 2c, and [(M−3 H)+][AlCl−4] 3 with the neutral hydrocarbon 1 reveals only small differences in bond lengths and angles, but establishes solvation contacts, π(η6)⋅⋅⋅K+ coordination in the polymer 2b, the flattening of one molecular half in the trihydropyren cation of 3 and ten H-bonds CH⋅⋅⋅Cl to the AlCl4− counter anion of 3. DFT/NBO Charge distributions, calculated based on the experimental structural parameters, show charge accumulation in the propanediyl bridges as well as in the peripheral naphthalene C−C bonds of the radical anions. The largest changes result expectedly for the formally triply dehydrogenated 1, i.e. the trihydropyren cation of 3, with two slightly positive and partly considerably less negative π-centers.