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2,3-Didehydro-1,4-benzoquinone. A Quantum Thermochemical Study

Cramer, C. J.
J. Chem. Soc., Perkin Trans. 2 1999, 2273.

Correlated electronic structure calculations at single and multireference levels of theory have been carried out for several neutral and radical anion states of 2,3-didehydro-1,4-benzoquinone, a quinone analog of o-benzyne. The molecule is predicted to be a ground-state singlet (1A1) with a 298 K heat of formation of 200.6 kJ/mol, a heat of hydrogenation (1 eq) of -323.5 kJ/mol, and an electron affinity of 1.95 eV; the latter quantity is in good agreement with an experimental value of 1.86 eV. The lowest energy triplet (13B2), derived from an in-plane pi to pi* excitation, is predicted to be 2.23 eV higher in energy than the singlet. The singlet and triplet states have biradical stabilization energies of 2.01 and -0.22 eV, respectively. Other triplet states derived from excitations involving the out-of-plane pi system are also examined. A recent photoelectron spectrum of the radical anion is interpreted, and a poorly resolved feature is proposed to correspond to the singlet (1A1) ground state of 2,6-didehydro-1,4-benzoquinone. Technical aspects governing the suitability of various levels of theory are also discussed.

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