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Volumn 25, Issue 2, 2006, Pages 358-367

Conformational analysis of ferrocene-containing alcohols. A density functional study of weak OH⋯Fe interactions

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONS; ELECTROSTATICS; IRON; NUCLEAR MAGNETIC RESONANCE; PROBABILITY DENSITY FUNCTION; SUBSTITUTION REACTIONS; TOPOLOGY;

EID: 31544471419     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om050810p     Document Type: Article
Times cited : (12)

References (102)
  • 11
    • 16244423722 scopus 로고    scopus 로고
    • and references therein
    • (c) Bühl, M.; Grigoleit, S. Organometallics 2005, 24, 1516-1527, and references therein.
    • (2005) Organometallics , vol.24 , pp. 1516-1527
    • Bühl, M.1    Grigoleit, S.2
  • 14
    • 0000126044 scopus 로고    scopus 로고
    • Togni, A., Halterman, R. L., Eds.; Wiley-VCH: Weinheim
    • (a) Togni, A. In Metallocenes: Synthesis and Reactivity, Togni, A., Halterman, R. L., Eds.; Wiley-VCH: Weinheim, 1998; Vol. 2, p 685.
    • (1998) Metallocenes: Synthesis and Reactivity , vol.2 , pp. 685
    • Togni, A.1
  • 27
  • 30
    • 31544471759 scopus 로고    scopus 로고
    • note
    • Generated automatically according to the procedure implemented in Gaussian 03.
  • 57
    • 31544465859 scopus 로고    scopus 로고
    • note
    • 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.
  • 58
    • 31544483252 scopus 로고    scopus 로고
    • note
    • It was reported that there was no minimum found that corresponds to structure 1a (M = Fe). See ref 5.
  • 59
    • 31544456996 scopus 로고    scopus 로고
    • note
    • 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.
  • 64
    • 0001064542 scopus 로고
    • 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.
    • (1994) Organometallics , vol.13 , pp. 3532-3543
    • Braga, D.1    Grepioni, F.2    Sabatino, P.3    Desiraju, G.R.4
  • 65
    • 31544469163 scopus 로고    scopus 로고
    • 1 mDyne/Å = 100 N/m
    • 1 mDyne/Å = 100 N/m.
  • 66
    • 31544433623 scopus 로고    scopus 로고
    • note
    • -1. See ref 3a.
  • 75
    • 8344253560 scopus 로고    scopus 로고
    • -1 for M = Ru (this work) and Fe, respectively (Grigoleit, S.; Bühl, M. Chem. Eur. J. 2004, 10, 5541-5552).
    • (2004) Chem. Eur. J. , vol.10 , pp. 5541-5552
    • Grigoleit, S.1    Bühl, M.2
  • 76
  • 77
    • 31544438760 scopus 로고    scopus 로고
    • note
    • 2O⋯HOH) is 20-30 times larger than the corresponding values in the ferrocenylmethanol conformers.
  • 78
    • 31544439036 scopus 로고    scopus 로고
    • note
    • This value is in a range where intramolecular dihydrogen bonding could be operative (1.6-2.1 Å).
  • 81
    • 31544464272 scopus 로고    scopus 로고
    • 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.
  • 84
    • 31544461721 scopus 로고    scopus 로고
    • note
    • 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.
  • 88
    • 31544465167 scopus 로고    scopus 로고
    • note
    • However, some of the rotamers converged back to a, b, or c conformation.
  • 96
    • 31544451744 scopus 로고    scopus 로고
    • 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.
  • 100
    • 31544473671 scopus 로고    scopus 로고
    • note
    • 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.
  • 102
    • 31544460310 scopus 로고    scopus 로고
    • note
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.