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31544465859
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note
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The OH group in la may rotate about the C-O bond to give one more rotamer, but during the geometry optimization this rotamer converged back to 1a.
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58
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31544483252
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note
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It was reported that there was no minimum found that corresponds to structure 1a (M = Fe). See ref 5.
-
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59
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31544456996
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These distances are somewhat sensitive to the basis set employed in the optimization; e.g., when optimized at BP86/AEK(+), d(Fe⋯HO) = 2.978 Å is obtained for 1a. The nonaugmented AE1 basis, which we used for the subsequent optimizations, is thus likely to underestimate the OH⋯ Fe distance somewhat in absolute terms; our conclusions are based on relative trends, however, which should be much less affected by this issue.
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60
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0010923811
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0001064542
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The most common type of hydrogen bonds in the solid state is intermolecular hydrogen bonding of the OH⋯O type. See: Braga, D.; Grepioni, F.; Sabatino, P.; Desiraju, G. R. Organometallics 1994, 13, 3532-3543.
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65
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31544469163
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1 mDyne/Å = 100 N/m
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1 mDyne/Å = 100 N/m.
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66
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31544433623
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note
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0000066725
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8344253560
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77
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31544438760
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-
note
-
2O⋯HOH) is 20-30 times larger than the corresponding values in the ferrocenylmethanol conformers.
-
-
-
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78
-
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31544439036
-
-
note
-
This value is in a range where intramolecular dihydrogen bonding could be operative (1.6-2.1 Å).
-
-
-
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81
-
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31544464272
-
-
note
-
s-symmetrical form (which has no BCP between H atoms) is only 0.4 kcal/mol above eclipsed 1b; this value is smaller than the intrinsic rotational barrier in ferrocene (ca. 1 kcal/mol), suggesting that there is no attractive H⋯H interaction in 1b.
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31544461721
-
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note
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This notion is supported by the fact that at the CP-opt level, which is inherently free of BSSE, a comparable ferrocene + water interaction energy, -0.9 kcal/mol, and very similar relative energies for 1a - e compared to those from Table 1 are obtained.
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0000592344
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31544465167
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note
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However, some of the rotamers converged back to a, b, or c conformation.
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90
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0001580673
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See e.g.: (a) Ferguson, G.; Gallagher, J. F.; Glidewell, C.; Zakaria, C. M. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1993, 49, 967-971.
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31544451744
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note
-
Note that the absence of a bond path does not mean the absence of any interaction, but rather the absence of interactions strong enough to leave their imprint on the topology of the electron density. The latter, in our case, appears to be quite insensitive to the basis set employed on the OH moiety: we performed additional geometry optimizations for 1a, 4a, and 5 using the 6-31G** basis on OH, i.e., with a set of polarization functions on the critical H (for 1a also with 6-311G** and 6-311+G** on this moiety); in no case did topological analysis show a bond path between OH and Fe.
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97
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0344894536
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See e.g.: (a) Nguyen, P.; Gomez-Elipe, P.; Manners, I. Chem. Rev. 1999, 99, 1515-1548.
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(1999)
Chem. Rev.
, vol.99
, pp. 1515-1548
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Nguyen, P.1
Gomez-Elipe, P.2
Manners, I.3
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99
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0030900382
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For example, the parent [2]ferrocenophane: Nelson, J. M.; Nguyen, P., Petersen, R.; Rengel, H.; Macdonald, P. M.; Lough, A. J.; Manners, I.; Raju, N. P.; Greedan, J. E.; Barlow, S.; O'Hare, D. Chem. Eur. J. 1997, 3, 573-584.
-
(1997)
Chem. Eur. J.
, vol.3
, pp. 573-584
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-
Nelson, J.M.1
Nguyen, P.2
Petersen, R.3
Rengel, H.4
Macdonald, P.M.5
Lough, A.J.6
Manners, I.7
Raju, N.P.8
Greedan, J.E.9
Barlow, S.10
O'Hare, D.11
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100
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31544473671
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note
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2ρ are also obtained when the augmented 6-31+G(d,p) basis is used for the OH group in the geometry optimization, even though the optimized Fe⋯H distance is somewhat elongated to 2.539 Å.
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-
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101
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0035848467
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- and hydrogen-bond donors: Alkorta, I.; Rozas, I.; Elguero, J. J. Mol. Struct. (THEOCHEM) 2001, 537, 139-150.
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(2001)
J. Mol. Struct. (THEOCHEM)
, vol.537
, pp. 139-150
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Alkorta, I.1
Rozas, I.2
Elguero, J.3
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102
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31544460310
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note
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At the BSSE-free CP-opt level, the relative energies of 13a, 13b, and 13c are 0, 1.3, and 2.2 kcal/mol, respectively.
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