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Volumn 3, Issue 3, 2001, Pages 329-332

In Search of Catalytically Active Species in the Surfactant-Mediated Biphasic Alkene Epoxidation with Mimoun-Type Complexes

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ARTICLE;

EID: 0003298969     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006775u     Document Type: Article
Times cited : (32)

References (62)
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    • (c) Mimoun, H. Angew. Chem. 1982, 94, 750; Angew. Chem., Int. Ed. Engl. 1982, 21, 734.
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  • 8
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    • (c) Mimoun, H. Angew. Chem. 1982, 94, 750; Angew. Chem., Int. Ed. Engl. 1982, 21, 734.
    • (1982) Angew. Chem., Int. Ed. Engl. , vol.21 , pp. 734
  • 9
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    • Sundermeyer, J. Angew. Chem. 1993, 105, 1195; Angew. Chem., Int. Ed. Engl. 1993, 32, 1144.
    • (1993) Angew. Chem. , vol.105 , pp. 1195
    • Sundermeyer, J.1
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    • Sundermeyer, J. Angew. Chem. 1993, 105, 1195; Angew. Chem., Int. Ed. Engl. 1993, 32, 1144.
    • (1993) Angew. Chem., Int. Ed. Engl. , vol.32 , pp. 1144
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    • (a) Gisdakis, P.; Antonczak, S.; Köstlmeier, S.; Herrmann, W. A.; Rösch, N. Angew. Chem. 1998, 110, 2333; Angew. Chem., Int. Ed. Engl. 1998, 37, 2211.
    • (1998) Angew. Chem., Int. Ed. Engl. , vol.37 , pp. 2211
  • 35
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    • N2 reactions, (ii) pericyclic reactions, for instance, Diels-Alder reactions, and (iii) reactions with a coarctate TS topology such as olefin epoxidation with dioxiranes. 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. (b) Herges, R. J. Chem. Inf. Comput. Sci. 1994, 34, 91. (Matrix Presented)
    • (1994) Angew. Chem. , vol.106 , pp. 261
    • Herges, R.1
  • 36
    • 0028259829 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 dioxiranes. 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. (b) Herges, R. J. Chem. Inf. Comput. Sci. 1994, 34, 91. (Matrix Presented)
    • (1994) J. Chem. Inf. Comput. Sci. , vol.34 , pp. 91
    • Herges, R.1
  • 39
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    • 0442302443 scopus 로고    scopus 로고
    • note
    • 3 ligand. Moreover, the complex protonated anywhere can react at several positions, which tremendously increases the number of isomers to be taken into account in a systematic study. With finite computational resources, we have been able to investigate the influence of protonation at the cis position and olefin attack at the trans position of the protonated peroxo moiety (Scheme 1). We chose this approach since the protonation at the peroxo moiety will have the strongest effect on the energy of the σ*(O-O) orbital.
  • 41
    • 0442270894 scopus 로고    scopus 로고
    • note
    • For geometry optimizations, Becke's three-parameter hybrid functional (B3, ref 20) together with the correlation functional of Lee, Yang, and Parr (LYP, ref 21) were employed as implemented in Guussian 98 (ref 22). Our standard basis set II (ref 23) was used, which consists of relativistic small-core ECPs (ref 24) and a (441/2111/31) valence basis set for Mo, while the 6-31G(d) (ret 25) all-electron basis set was employed for the other atoms. All stationary points were characterized by the calculation of vibrational frequencies. Energies reported have been corrected with respect to unsealed zero-point energies (ZPE). Improved total energies were calculated at the B3LYP level using the same ECP and valence basis set at Mo, but totally uncontracted and augmented with one set of f-type polarization functions (ref 26), together with the 6-31+G(d) basis set at the other atoms (ref 27). This basis-set combination is denoted III+ (ref 19).
  • 52
    • 0442302435 scopus 로고    scopus 로고
    • note
    • Note that experimental free-enthalpy values might differ from the calculated energies. For instance, the coordination of the aqua ligand with the metal is an isokinetic reaction, i.e., the entropic contribution to the free enthalpy partially compensates the enthalpic stabilization. Solvation effects were not explicity taken into account in our study because the molecules are too large. Furthermore, there is a basis-set-superposition error (BSSE), which is, however, expected to be very small since diffuse basis functions have been employed for energy calculations.
  • 53
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    • note
    • The most significant influence of the solvent can be expected for the protonated complexes. Since TS 5 is larger than reactant 5 and the positive total charge is therefore better stabilized in TS 5 than in 5, the activation energy will probably be underestimated. Furthermore, the presence of the counterion might increase the activation barrier.
  • 58
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    • (a) Thiel, W. R.; Priermeyer, T. Angew. Chem. 1995, 107, 1870; Angew. Chem., Int. Ed. Engl. 1995, 16, 1737.
    • (1995) Angew. Chem., Int. Ed. Engl. , vol.16 , pp. 1737


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.