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39
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85031061014
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note
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Likewise, according to the ref. 11, the DFT calculations agree best with the experimental results.
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40
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33748614674
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ZPE-s scaled by a factor of 0.989, as recommended for the Becke3LYP/6-311G(3df,2p) level, see:C.W. Bauschlicher Jr., H. Partridge, J. Chem. Phys. 103 (1995) 1788-1791.
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43
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85031050038
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note
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In the cases of 22e, 22g, 22h and 22r, the 2Pz orbital contribution is not equal to zero and was considered. This result is explained by the non-planearity of the aromatic ring (dihedral angle C(6)-C(1) -C(2) -C-3)(°), 22e: 0.49; 22g: 0.09; 22h: 0.7; 22r: 0.26).
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44
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0033515492
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For similar deformations in 2-pyridyl cation, see:F.C. Gozzo, M.N. Eberlin, J. Org. Chem. 64 (1999) 2188-2193.
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Gozzo, F.C.1
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45
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85031060636
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note
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13C coupling constants with those of model compounds suggested a cumulenic character for o-benzyne, see ref. 12b.
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46
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85031063610
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note
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-1 (Becke3LYP/ 6-311 + G(d,p)).
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47
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4544226816
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Wiley, New York
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M.B. Smith, J. March, J. March's Advanced Organic Chemistry, fifth ed., Wiley, New York, 2001, p. 368.
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J. March's Advanced Organic Chemistry, Fifth Ed.
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Smith, M.B.1
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49
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Dmitrienko, G.I.5
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51
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85031062968
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note
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+,).
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53
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85031056152
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note
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The structures of substituted benzenes calculated at the B3LYP/6-311G(d,p) level are in good agreement with experiment.
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54
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9744224621
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and the references cited therein
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For the energy of the 1,2-didehydrogenation of benzene, MP2/6-311G(d,p), QCISD/6-311G(d,p), CCSD(T)/6-311G(d,p) and BLYP/6-311G* calculations produce the values of 86.1, 91.2, 86.8 and 82.8kcal/mol, respectively, see: ref. 14c. The previously CCSD(T)/6-31G* reaction energy was of 91.00kcal/mol, see ref. 141; and at MP2/6-31G*//MP2/6-31G* level, 95.2 kcal/mol, see: ref. 14j. The experimental estimate value is 86.6(3.0 kcal/mol (at T = 298 K), see:P.G. Wenthold, R.R. Squires, J. Am. Chem. Soc. 116 (1994) 6401-6412. and the references cited therein.
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Wenthold, P.G.1
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85031050113
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note
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Much to our surprise, all attempts of cycloaddition conducted on 4-bromonitrobenzene and 4-bromobenzonitrile with 2-methylene-1,3-dioxepane failed to give the corresponding benzocyclobutanone dialkyl ketals. The starting material was recovered in each cases.
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56
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Wooward, R.B.1
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84987083701
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Similarly, studies concerning the [2s + 2a] cycloaddition of acetylene to ethylene to give cyclobutene led to an high transition state (75 kcal/mol), see:B.A. Hess Jr., L.J. Schaad, D.N. Reinhoudt, Int. J. Quant. Chem. 29 (1986) 345-350.
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Hess B.A., Jr.1
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62
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37049090527
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The [2 + 2] cycloaddition reactions of cyclopentyne and acetylene with ethylene are predicted to take place stepwise through diradical intermediates, see:S. Olivella, M.A. Pericàs, A. Riera, A. Solé, J. Chem. Soc., Perkin Trans. II (1986) 613-617.
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J. Chem. Soc., Perkin Trans. II
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Olivella, S.1
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84941997676
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(d) T. Hosoya, T. Hasegawa, Y. Kuriyama, T. Matsumoto, K. Suzuki, Synlett (1995) 177-179.
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Hosoya, T.1
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(e) T. Hosoya, T. Hamura, Y. Kuriyama, M. Miyamoto, T. Matsumoto, K. Suzuki, Synlett (2000) 520-522.
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85031062952
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note
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2 = 0.38.
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79
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85005470381
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J.A. Pople, A.P. Scott, M.W. Wong, L. Radom, Isr. J. Chem. 33 (1993) 345-350.
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