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At the RHF/6-31G(d) level used for structure determinations, there is a shallow minimum with the phenol group rotated to the bottom of the molecule. In contrast with the chalconide surfaces, an MP2/EXT calculation at the barrier for this rotation shows a lower energy than at the minimum, so this structure is omitted from Figure 1 as being probably nonexistent.
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23
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31
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33646512943
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note
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-1 above a minimum energy structure with unequal PO axial bonds, namely 1.756 and 2.275 Å, with an O-P-O angle of 167.6°. MP2/6-31G(d) optimization starting at this unsymmetrical RHF geometry gives the symmetric pentacoordinate structure shown in Figure 3.
-
-
-
-
32
-
-
33646498016
-
-
note
-
3 minima, so these minima are omitted from Figures 3 and 4 as being probably nonexistent isomers.
-
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-
-
33
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33646521416
-
-
note
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-1. Since MP2/EXT single-point calculations on this transition state lie below the energy of this tetracoordinate ion, this minimum is omitted from Figure 3 as being probably nonexistent. Ch = S shows no such minimum, as removal of the proton from the phenol parent's structure followed by geometry optimization leads directly to the pentacoordinate ion.
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35
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