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In the case of BHQ, the EPR spectral parameters of the observed radicals were consistent with the phenoxyl radical centered on the hindered oxygen atom. Actually, the spectrum of the phenoxyl radical showed coupling of the unpaired electron with the two meta-protons (0.88 G) and with the remaining hydroxyl proton (1.40 G). The formation of the other possible species, with the radical centered on the oxygen in position 4, can be discarded because larger splittings (ca. 6.5 G) from the protons in 3 and 5 would be expected in this case.
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The increase of the hfs constants at the nuclei of the para substituent observed in HFP can be explained on the basis of the polar mesomeric structure H involving spin delocalization on the substituent.
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27 on the equilibrium between a 2,6-di-tert-butyl substituted phenol and an unhindered phenol has been previously investigated. On changing the solvent from benzene to HBA solvent, the BDEs were found to increase by ca. 2 kcal/mol for phenols without ortho substituents, while in 2,6-di-tert-butyl substituted phenols they seem to be substantially unaffected. This behavior has been interpreted by admitting that the BDE increase observed in HBA solvents is essentially due to the solvation of the hydroxylic hydrogen which stabilizes the phenol, leaving the energy of the phenoxyl radical unaltered.
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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 J.A., Jr.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.51
Chen, W.52
Wong, M.W.53
Andres, J.L.54
Gonzalez, C.55
Head-Gordon, M.56
Replogle, E.S.57
Pople, J.A.58
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