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Volumn 691, Issue 24-25, 2006, Pages 5312-5325

Mechanistic comparison of ruthenium olefin metathesis catalysts: DFT insight into relative reactivity and decomposition behavior

Author keywords

Decomposition; DFT; Mechanism; Metathesis; Phoban catalyst

Indexed keywords

CATALYST ACTIVITY; DECOMPOSITION; OLEFINS; PROBABILITY DENSITY FUNCTION; REACTION KINETICS; RUTHENIUM;

EID: 33751373293     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jorganchem.2006.08.075     Document Type: Article
Times cited : (55)

References (114)
  • 1
    • 1442360753 scopus 로고    scopus 로고
    • For recent reviews on olefin metathesis see:. Grubbs R.H. (Ed), Wiley-VCH, Weinheim, Germany
    • For recent reviews on olefin metathesis see:. In: Grubbs R.H. (Ed). Handbook of Metathesis (2003), Wiley-VCH, Weinheim, Germany
    • (2003) Handbook of Metathesis
  • 92
    • 0034700583 scopus 로고    scopus 로고
    • For related transformations on substituted metallocyclobutanes see:
    • For related transformations on substituted metallocyclobutanes see:. Pietrazuk C., and Fischer H. Chem. Commun. (2000) 2463
    • (2000) Chem. Commun. , pp. 2463
    • Pietrazuk, C.1    Fischer, H.2
  • 97
    • 0001285962 scopus 로고
    • For related transformations on other metallacyclobutanes see:
    • For related transformations on other metallacyclobutanes see:. McLain S.J., Wood C.D., and Schrock R.R. J. Am. Chem. Soc. 99 (1977) 3519
    • (1977) J. Am. Chem. Soc. , vol.99 , pp. 3519
    • McLain, S.J.1    Wood, C.D.2    Schrock, R.R.3
  • 106
    • 0004324840 scopus 로고
    • Seminario J.M., and Politzer P. (Eds), Elsevier, Amsterdam, The Netherlands
    • Delley B. In: Seminario J.M., and Politzer P. (Eds). Modern Density Functional Theory: A Tool for Chemistry. Theoretical and Computational Chemistry vol. 2 (1995), Elsevier, Amsterdam, The Netherlands
    • (1995) Theoretical and Computational Chemistry , vol.2
    • Delley, B.1
  • 108
    • 33751364153 scopus 로고    scopus 로고
    • note
    • It should be noted that due to the symmetry of the Phobcat ruthenacyclobutane intermediate, III-4 and III′-4 are equivalent.
  • 109
    • 33751362702 scopus 로고    scopus 로고
    • note
    • 3 (Phoban-Cy concentration is higher than PCy3 concentration, however); and (ii) catalysis with Phobcat is initially slower compared to the first-generation catalyst.
  • 110
    • 33751354662 scopus 로고    scopus 로고
    • note
    • -1, respectively (1-octene: Ru = 9000, but 18 000 for the latter). While the traditional Grubbs catalysts do not show a sign of initiation under these conditions, the S-shaped curve of the plot of product formation over time clearly indicates for Phobcat the slower transformation of the starting benzylidene complex to an alkylidene in the catalytic cycle. Accordingly, the fastest TOF is reached within the first minute for the two Grubbs catalysts and only around 3-5 min for Phobcat.
  • 113
    • 33751378446 scopus 로고    scopus 로고
    • note
    • These calculations have been confirmed experimentally by preliminary 1H NMR studies. Full details of these studies will be disclosed in due course.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.