Hexakis(3,6-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)cyclohexane: Closed-Shell [6]Radialene or Open-Shell Hexa-Radicaloid?

A star-shaped hexaquinocyclohexane molecule 4 c is reported, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4 o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5±4.3 kJ mol-1 at room temperature from the hexa-radical form 4 o to the contorted [6]radialene form 4 c, because the transformation needs to overcome large steric repulsion between the neighboring phenoxyl units. Compound 4 c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9 %. This study demonstrates the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process.