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Volumn 128, Issue 39, 2006, Pages 13017-13025

Hafnocene catalysts for selective propylene oligomerization: Efficient synthesis of 4-methyl-1-pentene by β-methyl transfer

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST PRECURSORS; HAFNOCENE COMPLEXES; METHYL TRANSFER; PROPYLENE OLIGOMERIZATION;

EID: 33749534860     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja063717g     Document Type: Article
Times cited : (37)

References (58)
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    • (a) TPX, Mitsui Chemicals, Inc. http://www.mitsuichemicals.com/tpx.htm.
  • 16
    • 33749516747 scopus 로고    scopus 로고
    • (The Dow Chemical Company) U.S. Patent 4,695,669, 1987
    • (a) Stevens, J. C.; Fordyce, W. A. (The Dow Chemical Company) U.S. Patent 4,695,669, 1987.
    • Stevens, J.C.1    Fordyce, W.A.2
  • 17
    • 33749525776 scopus 로고    scopus 로고
    • (The Dow Chemical Company) U.S. Patent 4,855,523, 1989
    • (b) Stevens, J. C.; Fordyce, W. A. (The Dow Chemical Company) U.S. Patent 4,855,523, 1989.
    • Stevens, J.C.1    Fordyce, W.A.2
  • 18
    • 33749511360 scopus 로고    scopus 로고
    • (Idemitsu Kosan Company) U.S. Patent 4,814,540, 1989
    • Watanabe, M.; Kuramoto, M. (Idemitsu Kosan Company) U.S. Patent 4,814,540, 1989.
    • Watanabe, M.1    Kuramoto, M.2
  • 21
    • 0000322995 scopus 로고
    • Two alternative mechanisms for the formation of 4-methyl-1-pentene are conceivable. One involves double 2,1-insertion of propylene into a metalhydride bond followed by β-hydride elimination (ref 1c). This mechanism is ruled out on the basis of the assumption that double 2,1-insertion within a constrained peralkylmetallocene ligand sphere is sterically prohibitive. The other alternative involves the oxidative coupling of two propylene units at a divalent metallocene fragment to give 2,4-dimethylmetallacyclopentane followed by β-hydride elimination/reductive elimination (McLain, S.; Sancho, J.; Schrock, R. R. J. Am. Chem. Soc. 1980, 102, 5610-5618;
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 5610-5618
    • McLain, S.1    Sancho, J.2    Schrock, R.R.3
  • 22
    • 37049090582 scopus 로고
    • Takahashi, T.; Fujimori, T.; Seki, T.; Saburi, M.; Uchida, Y.; Rousset, C. J.; Negishi, E. J. Chem. Soc., Chem. Commun. 1990, 182-183). This second alternative can be excluded because it requires the formation of divalent hafnocene species under the present conditions. Moreover, characteristic byproducts of such an oxidative coupling/β-H elimination/reductive elimination process are absent (2,3-dimethyl-1-butene, 4-methyl-2-pentene, 1-hexene, 2-hexene), and the formation of higher oligomers cannot be explained by this process.
    • (1990) J. Chem. Soc., Chem. Commun. , pp. 182-183
    • Takahashi, T.1    Fujimori, T.2    Seki, T.3    Saburi, M.4    Uchida, Y.5    Rousset, C.J.6    Negishi, E.7
  • 45
    • 33749513309 scopus 로고    scopus 로고
    • note
    • 2/MAO was mentioned in ref 10.
  • 49
    • 33749523981 scopus 로고    scopus 로고
    • note
    • When β-H elimination becomes negligible, the Flory-Schulz theory is applicable; see ref 9b.
  • 50
    • 33749537773 scopus 로고    scopus 로고
    • note
    • 3.
  • 53
    • 1142280731 scopus 로고    scopus 로고
    • For a recent example of a dramatic effect on metallocene reactivity by a ring substituent pattern, see: Pool, J. A.; Lobkovsky, E.; Chirik, P. J. Nature 2004, 427, 527-530.
    • (2004) Nature , vol.427 , pp. 527-530
    • Pool, J.A.1    Lobkovsky, E.2    Chirik, P.J.3
  • 54
    • 0003056447 scopus 로고
    • For a review on bulky cyclopentadienyl ligands, see: Okuda, J. Top. Curr. Chem. 1992, 160, 97-145.
    • (1992) Top. Curr. Chem. , vol.160 , pp. 97-145
    • Okuda, J.1
  • 58
    • 3342961533 scopus 로고    scopus 로고
    • Mathematica 5.0; Wolfram Research, Inc. http://www.wolfram.com.
    • Mathematica 5.0


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.