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Volumn 105, Issue 19, 2001, Pages 4765-4772

Ethylene epoxidation with tungsten diperoxo complexes: Is relativity the origin of reactivity?

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDATION;

EID: 0035901825     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0100497     Document Type: Article
Times cited : (28)

References (121)
  • 7
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    • note
    • 3)] is only one of the active species. For instance, protonated diperoxo species, which might exist in the catalytic system in small concentrations, are more reactive than the parent complex (ref 8d).
  • 26
    • 0000849653 scopus 로고
    • Ti-catalyzed olefin epoxidation has also theoretically been studied; for example, see: (a) Wu, Y. D.; Lai, D. K. W. J. Am. Chem. Soc. 1995, 117, 11327.
    • (1995) J. Am. Chem. Soc. , vol.117 , pp. 11327
    • Wu, Y.D.1    Lai, D.K.W.2
  • 35
    • 0000360109 scopus 로고
    • N2 reactions, (ii) pericyclic reactions, for instance Diels-Alder reactions, and (iii) reactions with a coarctate TS topology such as olefin epoxidation with peroxy acids (ref 15) or dioxiranes (ref 16). Reactions of the latter class proceed by breaking and making two bonds at one or more atoms at a time. For details, see: (a) Herges, R. Angew. Chem. 1994, 106, 261.
    • (1994) Angew. Chem. , vol.106 , pp. 261
    • Herges, R.1
  • 75
    • 0003990093 scopus 로고
    • Internal Report (in Dutch); Vrije Universiteit Amsterdam: The Netherlands
    • Krijn, J. G.; Baerends, E. J. Fit Functions in the HFS-Method; Internal Report (in Dutch); Vrije Universiteit Amsterdam: The Netherlands, 1984.
    • (1984) Fit Functions in the HFS-Method
    • Krijn, J.G.1    Baerends, E.J.2
  • 92
    • 19944422170 scopus 로고    scopus 로고
    • Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York
    • (e) Almlöf, J.; Gropen, O. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 1996; Vol. 8, p 203.
    • (1996) Reviews in Computational Chemistry , vol.8 , pp. 203
    • Almlöf, J.1    Gropen, O.2
  • 96
    • 0011400116 scopus 로고    scopus 로고
    • note
    • We have chosen a definition of the Dirac equation with (Matrix Presented) instead of (Matrix Presented) to align the nonrelativistic and relativistic energy scales.
  • 109
    • 0011507281 scopus 로고    scopus 로고
    • note
    • The transition states show a significant anomeric effect, which was pointed out in our previous studies (ref 8ab). In the TS, the phosphorus-oxygen bond (P-O6) has a synperiplanar orientation to the active metalladioxirane moiety (M, O2, O3; see Figure 1) because the lone pair of O6 with an antiperiplanar orientation to the active metalladioxirane moiety supports the cleavage of the Mo-O3 bond.
  • 110
    • 0011462272 scopus 로고    scopus 로고
    • note
    • There is no experimental activation energy available because the kinetic data presented in the pioneering work (ref 2b) were interpreted in favor of the wrong mechanism. BP86 activation barriers for the epoxidation of olefins with organic peracids (ref 15) are several kcal/mol lower than B3LYP values, which in turn underestimate experimental activation energies. In the present work, we employ the BP86 functional because both the fragment-based energy-decomposition scheme and BP86 are implemented in the ADF package while the hybrid functional is not.
  • 114
    • 0011494546 scopus 로고    scopus 로고
    • note
    • The relation among the extent of reaction, the extent of asymmetry, and the electronic character at the TS for the epoxidation of various α olefins with peroxyformic acid and dioxirane was recently studied and the effects on reactivity were pointed out; for details, see ref 15q.
  • 115
    • 0002429093 scopus 로고
    • Edwards, J. O., Ed.; Interscience: New York
    • The attack of the σ*-(O-O) Orbital of electrophilic oxidants was postulated by Edwards: (a) Edwards, J. O. In Peroxide Reaction Mechanisms; Edwards, J. O., Ed.; Interscience: New York, 1962; p. 67.
    • (1962) Peroxide Reaction Mechanisms , pp. 67
    • Edwards, J.O.1
  • 117
    • 0011402705 scopus 로고    scopus 로고
    • note
    • The geometries of TS- and TS+ were calculated by adding -0.1 and 0.1, respectively, of the eigenvector that corresponds to the negative eigenvalue of the force-constants matrix to the coordinates of the stationary point.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.