Abstract
Restricted and unrestricted (U) Hartree–Fock (HF), second-order Møller–Plesset perturbation (MP2), density functional (DF), hybrid HF/DF and semiempirical (half-electron (HE) method) models have been used to calculate adiabatic electron affinities (EAad values) of p- benzoquinone (I), p-benzoquinone imine (VI) and p-benzoquinone diimine (XI), as well as expectation values (〈S2〉) and spin density distributions in the radical anions of I, VI and XI. The AM1/AM1-HE and ab initio calculated structures are found to be in accord with each other. The ROHF/6-31G(d) method gave the poorest EAad result. The UHF and UMP2 wave functions were found to be substantially spin contaminated (for the radicals) and the accuracies of the EAad values calculated were also poor. The use of molecular energies obtained after spin annihilation did not lead to significant improvement of the UHF and UMP2 results. In contrast to the ROHF, UHF and UMP2 results, the DF(USVWN, UBVWN, UBLYP) and hybrid HF/DF(UB3LYP) methods, as well as the AM1-HE, gave much better results. The calculated EAad values decreased, as predicted by most of the models, in the order EAad(I) > EAad(VI) > EAad(XI). The differences in the EAs, EAad(I) − EAad(VI) and EAad(I) − EAad(XI), were consistently predicted to be about 8–9 and 17–18 kcal/mol, respectively, by the DF, B3LYP and AM1-HE models. The performance of the PM3 and SAM1 models was not as good as the AM1 model. Of all the methods tested, the B3LYP/6-311G(d,p) model is concluded to give the most accurate quantitative trend (I(42.6) > VI(33.1) > XI(23.7)) in EAad. The predicted trend in EA can satisfactorily be rationalized by the calculated LUMO orbital energies, atomic charges and spin density distributions. Analysis of the spin density data predicts that phenoxyl- and anilino-type radical anions predominate in the p-benzosemiquinones of I and XI, respectively, while both phenoxyl- and anilino-type radicals contribute to the structure of the p-benzosemiquinone of VI, with the anilino-type predominating.
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Acton, E.M., In Priebe, W. (Ed.) Anthracycline Antibiotics, ACS Symposium Series Vol. 574, American Chemical Society, Washington, DC, U.S.A., 1995, pp. 1–13.
Myers, C.E., Muinda, J.R.F., Zweier, J. and Sinha, B.K., J. Biol. Chem., 262 (1987) 11571, and references cited therein.
Lown, J.W., Chen, H.H. and Plambeck, J.A., Biochem. Pharmacol., 28 (1979) 2563. b. Lown, J.W., Chen, H.H. and Plambeck, J.A., Biochem. Pharmacol., 31 (1982) 575. c. Vavies, K.J.A., Doroshow, J.H. and Hochstein, H.P., FEBS Lett., 153 (1983) 227. d. Mimnaugh, E.G., Trush, M.A., Ciarrocchi, E.G., Lestingi, M., Fontana, M., Spadasi, S. and Montecucco, A., Biochem. J., 279 (1991) 141. e. Nafzinger, J., Auclair, C., Florent, J.C., Guillosson, J.J. and Monneret, C., Lechemie Res., 15 (1991) 709. f. Mimnaugh, E.G., Trush, M.A., Ginsburg, E. and Gram, T.E., Cancer Res., 42 (1982) 3574.
Abdella, B.R.J. and Fisher, J., J. Environ. Health Perspect., 64 (1985) 3.
Davies, K.J.A. and Doroshow, J.H., J. Biol. Chem., 261 (1986) 3060. b. Davies, K.J.A. and Doroshow, J.H., J. Biol. Chem., 261 (1986) 3068.
Favandon, K., Biochemie, 64 (1982) 457. b. Lown, J.W., Acc. Chem. Res., 15 (1982) 381. c. Dodd, N.J.F. and Mucherjee, T., Biochem. Pharmacol., 33 (1984) 379. d. Nohland, H. and Jordan, W., Biochem. Biophys. Res. Commun., 114 (1983) 197.
Mariam, Y.H. and Sawyer, A., J. Comput.-Aided Mol. Design, 10 (1996) 441.
Ziegler, T. and Gutsev, G.L., J. Comput. Chem., 13 (1992) 70.
Dewar, M.J.S., Hashmall, J.A. and Venier, C.G., J. Am. Chem. Soc., 90 (1968) 1953.
Dewar, M.J.S. and Rzepa, H.S., J. Am. Chem. Soc., 100 (1978) 784.
Cooper, C.D., Naft, W.T. and Compton, R.N., J. Chem. Phys., 63 (1975) 2752.
Heinis, T., Chowdhury, S., Scott, S.L. and Kebarle, P., J. Am. Chem. Soc., 110 (1988) 400. b. Chowdhury, S., Grimsrud, E.P. and Kebarle, P., J. Phys. Chem., 90 (1986) 2747.
Vosko, S.H., Wilk, L. and Nusair, M., Can. J. Phys., 58 (1980) 1200.
SPARTAN User's Guide, v. 4.0, Wavefunction, Irvine, CA, U.S.A., 1995.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gill, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Keith, T., Petersson, G.A., Montgomery, J.A., Raghavachari, K., Al-Laham, M.A., Zakrzewski, V.G., Ortiz, J.V., Foresman, J.B., Cioslowski, J., Stefanov, B.B., Nanayakkara, A., Challacombe, M., Peng, C.Y., Ayala, P.Y., Chen, W., Wong, M.W., Andres, J.L., Replogle, E.S., Gomperts, R., Martin, R.L., Fox, D.J., Binkley, J.S., Defrees, D.J., Baker, J., Stewart, J.P., Head-Gordon, M., Gonzalez, C. and Pople, J.A., GAUSSIAN, 94, Revision D.1, Gaussian Inc., Pittsburgh, PA, U.S.A., 1995.
Hehre, W.J., Radom, L., Schleyer, P.v.R. and Pople, J.A., Ab Initio Molecular Orbital Theory, Wiley, New York, NY, U.S.A., 1986. b. Levine, I.N., Quantum Chemistry, Prentice-Hall, Englewood Cliffs, NJ, U.S.A., 1993.
Møller, C. and Plesset, M.S., Phys. Rev., 46 (1934) 618. b. Pople, J.A., Binkley, J.S. and Seeger, R., Int. J. Quantum Chem. Quantum Chem. Symp., 10 (1976) 1.
Kohn, W. and Sham, L.J., Phys. Rev., A140 (1965) A1133. b. Pople, J.A., Gill, P.M.W. and Johnson, B.G., Chem. Phys. Lett., 199 (1992) 557.
GAUSSIAN94 User's Reference, Gaussian Inc., Pittsburgh, PA, U.S.A., 1994-1995.
Becke, A.D., Phys. Rev., A38 (1988) 3098.
Lee, C., Yang, W. and Parr, R.G., Phys. Rev., B37 (1988) 785.
Becke, A.D., J. Chem. Phys., 98 (1993) 5648.
Slater, J.C., Quantum Theory of Molecules and Solids, Vol. 4, McGraw-Hill, New York, NY, U.S.A., 1974.
Boesch, S.E. and Wheeler, R.A., J. Phys. Chem., 99 (1995) 8125.
Gordon, A.R. and Ford, R.A., The Chemist's Companion, Wiley, New York, NY, U.S.A., 1972, pp. 105–108.
Vollhardt, K.P.C., Organic Chemistry, Freeman, New York, NY, U.S.A., 1987, pp. 1189–1198.
Hehre, W.J., Radom, L., Schleyer, P.v.R. and Pople, J.A., Ab Initio Molecular Orbital Theory, Wiley, New York, NY, U.S.A., 1986, pp. 165–173.
Wheeler, R.A., J. Am. Chem. Soc., 116 (1994) 11048.
Robinson, H.H. and Kahn, S.D., J. Am. Chem. Soc., 112 (1990) 4728.
Qin, Y. and Wheeler, R.A., J. Chem. Phys., 102 (1995) 1687.
Schlegel, H.B., J. Chem. Phys., 84 (1986) 4530.
Baker, J., Scheiner, A. and Andzelm, J., Chem. Phys. Lett., 216 (1993) 380.
Cramer, C.J., Dulles, F.J., Giesen, D.J. and Almlof, J., Chem. Phys. Lett., 245 (1995) 165.
Neat, P. and Fessenden, R.W., J. Phys. Chem., 78 (1974) 523. b. West, P.R., Harman, L.S., Josephy, P.D. and Mason, R.P., Biochem. Pharmacol., 33 (1984) 2933.
Stone, T.J. and Waters, W.A., Proc. Chem. Soc., (1962) 253.
Schlegel, H.B., J. Chem. Phys., 92 (1988) 3075.
Chen, W. and Schlegel, H.B., J. Chem. Phys., 101 (1994) 5957.
Koopmans, T., Physica, 1 (1934) 104.
Lide, D.R. (Ed.), CRC Handbook of Chemistry and Physics, 76th ed., CRC Press, Boca Raton, FL, U.S.A., 1995-1996.
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Mariam, Y.H., Chantranupong, L. Electron affinities of p-benzoquinone, p-benzoquinone imine and p-benzoquinone diimine, and spin densities of their p-benzosemiq. J Comput Aided Mol Des 11, 345–356 (1997). https://doi.org/10.1023/A:1007903612053
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DOI: https://doi.org/10.1023/A:1007903612053