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Mono- and Diprotonation of Dihydropyrene, 2,7-Di-Tert-Butyldihydropyrene, and Their Conversion To Pyrenium Ions; Influence of the Radical Cation and Its Potential Utility in Nmr Assignments of the Arenium Ions of Readily Oxidizable Pahs#

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Parent dihydropyrene 1 and 2,7-di-tert-butyldihydropyrene 3 are monoprotonated with FSO3H/SO2ClF to give their persistent monoarenium ions 1H+ and 3H+ by the attack of proton at C-3 (peri to the ethano-bridge not at C-1 as previously suggested). Dihydropyrene 3 is diprotonated in FSO3H.SbF5 1:1 "Magic Acid"R/SO2ClF to give the symmetrical dication 3H2+2, similar diprotonation of 1 with "Magic Acid"/SO2ClF or with FSO3H.SbF5 (4:1)/SO2ClF gave the diprotonated species 1H2+2 in a mixture. NMR characteristics of the mono- and dications are discussed. On raising temperature or on prolonged cold storage, 1H+ and 3H+ are converted to,their corresponding pyrenium cations (2H+ and 4H+). Formation of 2H+ from 1 is more rapid than conversion of 3 to 4H+. Parent pyrenium cation was independently generated by protonation with FSO3H/SO2ClF. When a mixture of 2 and 1 is reacted with FSO3H/SO2ClF (dry ice/acetone temperature) only 2H+ is seen in the NMR (concomitant presence of the radical cation 1+. is inferred from EPR). Similar protonation of a mixture of 6-chlorochrysene 5 and 1 with FSO3H/SO2ClF leads to NMR observation of 1H+ (with concomitant presence of 5+.); on raising temperature 1H+ is converted to 2H+. The nature of the paramagnetic radical cation (RC) present in the arenium ion samples influences the position, and resolution of the NMR spectra. This approach may prove useful in NMR studies of large polycyclic aromatic hydrocarbons PAHs where concomitant RC formation greatly diminishes the quality of the NMR spectra.

Affiliations: 1: Department of Chemistry, Kent State University, Kent, OH 44242 U.S.A., Department of Life Sciences and Chemistry, Roskilde University, DK-4000 Roskilde, Denmark


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