Biphenalenylidene: the forgotten bistricyclic aromatic ene. A theoretical study.
The Lawesson reagent and P(2)S(5) mediated reductive coupling of phenalenone (6) gives LPAH peropyrene (5) in 47% and 54% yields. The mechanism of the reaction involves the formation of phenalenethione (10), Z- and E-1,1'-biphenalenylidene (3), and 9 as intermediates. The electrocyclization reaction of Z-3 to 9, followed by aromatization, gives 5. The results of an ab initio and DFT study of 3 and 2,2'-biphenalenylidene (12) are reported. E-3 and Z-3 have a diradical character with twist angles of 44.8 degrees and 57.8 degrees (at UB3LYP/6-311G**). Delta E(++)(Tot) = 10.2 kJ/mol and Delta G(++)(298) = 10.6 kJ/mol for E-3 <==> Z-3 diastereomerization. These unusually low energy barriers are due to the ground-state diradical destabilization and the aromatic stabilization of the transition state TS-3. Triplet Z-3 is higher in energy than singlets E-3 and Z-3 by 10.4 and 3.1 kJ/mol. In the concealed non-Kekulé 12, singlet 12 is more stable than the triplet by 1.3 kJ/mol. Singlet 12 is more stable than singlet E-3 by 2.0 kJ/mol, and orthogonal singlet TS-12 is lower in energy than singlet TS-3 by 6.0 kJ/mol. The energy barriers for the hexatriene-cyclohexadiene electrocyclization Z-3 --> 9 are Delta E(++)(Tot) = 94.8 and Delta G(++)(298) = 98.3 kJ/mol (at (U)B3LYP/6-31G). The reaction occurs thermally in a conrotatory mode.
Pogodin
Sergey
S
Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Agranat
Israel
I