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Estimated spin density on nitrogen = 41 ± 5% in an orbital whose p/s ratio is 6.1 ± 0.7; see ref 9.
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11
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To distinguish them from the more common class of π radicals in which the unpaired electron is in an orbital perpendicular to the local molecular framework.
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Reference 16
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The sources of error we have identified in Bordwell et al.'s. EC-measured O-H BDEs for phenols and N-H BDEs for anilines have been described: (a) Reference 16.
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See footnote a, Table 1.
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4344695098
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This revision has important implications since the calorimetric O-H BDE in 2,4,6-tri-tert-butylphenol of 81.24 kcal/mol26 has been used as the standard for all BDEs determined by the REqEPR technique,17d.27 and hence, all of these BDEs should be revised downward by 1 kcal/mol (and even lower for many phenols because of H-bonding to the benzene solvent used for REqEPR measurements).28 Interestingly, the 1 kcal/mol downward revision of the O-H BDE in phenol and α-tocopherol yields values of 87.3 and 77.3 kcal/mol, respectively, in full agreement with the results obtained by photoacoustic calorimetry.16.29
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These corrections to REqEPR-derived BDEs will be detailed in a forthcoming article.
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Estimated from data given in ref 16 for the phenol-benzene hydrogen bond.
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Since 443 K is just above the boiling point of tert-butylbenzene, reaction times were not shortened by raising the temperature for reasons of safety.
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58
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4344647134
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note
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3 In the data analysis, a pre-equilibration time was used to compensate for this feature.
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59
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4344662555
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note
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..4.12 The probable mechanisms by which these compounds are formed have been described.12 At least some of these products were present after heating the O-benzyl oxime ethers to 443 K for many weeks, but since they provide no useful information they will be ignored henceforth.
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Frisch, M.J.1
Trucks, G.W.2
Schlegel, H.B.3
Scuseria, G.E.4
Robb, M.A.5
Cheeseman, J.R.6
Zakrzewski, V.G.7
Montgomery Jr., J.A.8
Stratmann, R.E.9
Burant, J.C.10
Dapprich, S.11
Millam, J.M.12
Daniels, A.D.13
Kudin, K.N.14
Strain, M.C.15
Farkas, O.16
Tomasi, J.17
Barone, V.18
Cossi, M.19
Cammi, R.20
Mennucci, B.21
Pomelli, C.22
Adamo, C.23
Clifford, S.24
Ochterski, J.25
Petersson, G.A.26
Ayala, P.Y.27
Cui, Q.28
Morokuma, K.29
Malick, D.K.30
Rabuck, A.D.31
Raghavachari, K.32
Foresman, J.B.33
Cioslowski, J.34
Ortiz, J.V.35
Stefanov, B.B.36
Liu, G.37
Liashenko, A.38
Piskorz, P.39
Komaromi, I.40
Gomperts, R.41
Martin, R.L.42
Fox, D.J.43
Keith, T.44
Al-Laham, M.A.45
Peng, C.Y.46
Nanayakkara, A.47
Gonzalez, C.48
Challacombe, M.49
Gill, P.M.W.50
Johnson, B.G.51
Chen, W.52
Wong, M.W.53
Andres, J.L.54
Head-Gordon, M.55
Replogle, E.S.56
Pople, J.A.57
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Golstein, S.1
Czapski, G.2
Lind, J.3
Merényi, G.4
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