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Volumn 127, Issue 12, 2005, Pages 4510-4517

Regarding the mechanism of olefin metathesis with sol-gel-supported Ru-based complexes bearing a bidentate carbene ligand. Spectroscopic evidence for return of the propagating Ru carbene

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; COMPLEXATION; DECOMPOSITION; REACTION KINETICS; RUTHENIUM COMPOUNDS; SOL-GELS; STYRENE; TRANSITION METALS;

EID: 16244369421     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja042668+     Document Type: Article
Times cited : (106)

References (62)
  • 31
    • 2942631595 scopus 로고    scopus 로고
    • Grubbs, R. H., Ed.; VCH-Wiley: Weinheim, Germany, and references therein
    • Sanford, M. S.; Love, J. A. In Handbook of Olefin Metathesis; Grubbs, R. H., Ed.; VCH-Wiley: Weinheim, Germany, 2003; Vol. 1, pp 112-131, and references therein.
    • (2003) Handbook of Olefin Metathesis , vol.1 , pp. 112-131
    • Sanford, M.S.1    Love, J.A.2
  • 34
    • 0000025162 scopus 로고    scopus 로고
    • For related reports on supported Ru-based complexes bearing monodentate carbenes used for olefin metathesis, where a similar release/return scenario is suggested, see: (a) Barrett, A. G. M.; Cramp, S. M.; Roberts, R. S. Org. Lett. 1999, 1, 1083-1086.
    • (1999) Org. Lett. , vol.1 , pp. 1083-1086
    • Barrett, A.G.M.1    Cramp, S.M.2    Roberts, R.S.3
  • 38
    • 16244396808 scopus 로고    scopus 로고
    • Grubbs, R. H., Ed.; VCH-Wiley: Wienheim, Germany
    • Nguyen, S. T.; Trnka, T. M. In Handbook of Olefin Metathesis; Grubbs, R. H., Ed.; VCH-Wiley: Wienheim, Germany, 2003; Vol. 1, p 77.
    • (2003) Handbook of Olefin Metathesis , vol.1 , pp. 77
    • Nguyen, S.T.1    Trnka, T.M.2
  • 47
    • 0035800494 scopus 로고    scopus 로고
    • Another (not necessarily mechanistically related) observation indicating that alteration of the aryl substituents of an NHC ligand can have unexpected effects on the stability and reactivity of the derived Ru carbenes can be found in a recent synthesis of a related Ru carbene bearing 2,6-diisopropylphenyl substituents on the saturated NHC; a Ru hydride was isolated as a major byproduct. See: Furstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236-3253.
    • (2001) Chem. Eur. J. , vol.7 , pp. 3236-3253
    • Furstner, A.1    Ackermann, L.2    Gabor, B.3    Goddard, R.4    Lehmann, C.W.5    Mynott, R.6    Stelzer, F.7    Thiel, O.R.8
  • 48
    • 16244373114 scopus 로고    scopus 로고
    • note
    • See the Supporting Information for details.
  • 50
    • 16244421781 scopus 로고    scopus 로고
    • note
    • This compound is easily formed by ring-opening of commercially available cis-5-norbornene-endo-2,3-dicarboxylic anhydride with 2 equiv of the functionalized benzylic alcohol; for details, see ref 10.
  • 51
    • 16244405661 scopus 로고    scopus 로고
    • note
    • The value was calculated from the mass increase following functionalization of the glass surface.
  • 52
    • 16244423060 scopus 로고    scopus 로고
    • note
    • If stirring is allowed to proceed for a longer period, RCM proceeds to > 99% conversion for each catalyst. Reactions in Table 1 were stopped abruptly at 1 h simply by drawing the reaction mixture away from the catalyst pellet with a Pasteur pipet.
  • 56
    • 16244367826 scopus 로고    scopus 로고
    • Reference 8
    • (d) Reference 8.
  • 57
    • 16244403387 scopus 로고    scopus 로고
    • note
    • Mechanistic studies involving chiral Ru complex 3 (Chart 1) and its deuterated derivatives indicate that catalyst recovered in high yield (90%) after olefin metathesis represents unreleased Ru carbene. Thus, even with the less active chiral complex, bearing a bidentate and sterically bulky ligand, high activity can be achieved with ≤ 10% released carbene. See ref 4b.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.