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Volumn 125, Issue 33, 2003, Pages 10103-10109

Synthesis, structure, and activity of enhanced initiators for olefin metathesis

Author keywords

[No Author keywords available]

Indexed keywords

RING-OPENING METATHESIS POLYMERIZATIONS (ROMP);

EID: 0042020353     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027472t     Document Type: Article
Times cited : (343)

References (74)
  • 20
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    • note
    • For simplicity, this cycle represents a degenerate metathesis reaction.
  • 26
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    • note
    • (b) See also ref 4a.
  • 28
    • 0041679655 scopus 로고    scopus 로고
    • note
    • (b) See also ref 5.
  • 32
    • 0035803098 scopus 로고    scopus 로고
    • Photolysis of 1 was found to result in phosphine dissociation. It was suggested that this could be used to initiate ruthenium olefin metathesis catalysts, although such an approach to increasing initiation has not yet been published. Kunkely, H.; Vogler, A. Inorg. Chim. Acta 2001, 325, 179.
    • (2001) Inorg. Chim. Acta , vol.325 , pp. 179
    • Kunkely, H.1    Vogler, A.2
  • 40
    • 0033578944 scopus 로고    scopus 로고
    • Decomposition of complex 1 proceeds through the bimolecular coupling of the 14-electron intermediate. Thus, an increase in initiated complex will increase the decomposition rate. The decomposition of complex 2 is more complicated and several orders of magnitude slower than phosphine dissociation, For a discussion of catalyst decomposition, see: Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202.
    • (1999) J. Org. Chem. , vol.64 , pp. 7202
    • Ulman, M.1    Grubbs, R.H.2
  • 42
    • 0041679653 scopus 로고    scopus 로고
    • note
    • Crystals suitable for X-ray structure determination were obtained by vapor diffusion of pentane into a saturated benzene solution of 2, 7, and 9 at room temperature. Crystal data and structure refinement are given in Supporting Information as Table S23.
  • 50
    • 11644311048 scopus 로고
    • Values are for free phosphines. See: Tolman, C. A. Chem. Rev. 1977, 77, 313.
    • (1977) Chem. Rev. , vol.77 , pp. 313
    • Tolman, C.A.1
  • 51
    • 0042180315 scopus 로고    scopus 로고
    • note
    • 1 were obtained by magnetization transfer experiments, except for complex 4, which was determined using stoichiometric initiation with ethyl vinyl ether. The magnetization transfer technique is described in further detail in the Experimental Section. The Eyring plot from the initiation experiments with 4 is shown in Supporting Information as Figure S14.
  • 52
    • 0042681486 scopus 로고    scopus 로고
    • note
    • Ascribing a cone angle to an unsymmetrical phosphine is not strictly correct; however, cone angles are the most commonly used method for comparing steric size.
  • 53
    • 0042681487 scopus 로고    scopus 로고
    • note
    • FTX does not distinguish between σ-donor and π-back-bonding abilities. See ref 22 for discussion.
  • 54
    • 0001962511 scopus 로고
    • Chapman, N. B., Shorter, J., Eds.; Plenum: New York
    • Ewing, D. F. In Correlation Analysis in Chemistry; Chapman, N. B., Shorter, J., Eds.; Plenum: New York, 1978; pp 357-96.
    • (1978) Correlation Analysis in Chemistry , pp. 357-396
    • Ewing, D.F.1
  • 55
    • 0042180317 scopus 로고    scopus 로고
    • note
    • a than benzoic acid-derived Hammett constants.
  • 56
    • 0043181926 scopus 로고    scopus 로고
    • note
    • FTX. This plot is shown in Supporting Information as Figure S13.
  • 57
    • 0042681485 scopus 로고    scopus 로고
    • note
    • -1, is consistent with a dissociative mechanism, as is the case with the phosphine-bound complexes.
  • 58
    • 0041679652 scopus 로고    scopus 로고
    • note
    • 2 is described in the Experimental Section. The rate equation used in data analysis is described in Supporting Information. The assumptions made for this experiment are described in detail in ref 7b.
  • 59
    • 0042180316 scopus 로고    scopus 로고
    • note
    • Since these are ratios of two second-order rate constants, we expect them to be comparable despite the difference in temperature.
  • 65
    • 0041679650 scopus 로고    scopus 로고
    • note
    • Notably, the rate constants are reported as relative rate constants.
  • 66
    • 0041679651 scopus 로고    scopus 로고
    • note
    • Rate of reaction using complex 9 increases linearly with concentration of 13.
  • 68
    • 0000362257 scopus 로고
    • Hanessian, S.; Leger, R. J. Am. Chem. Soc. 1992, 114, 3115. See also: Kirkland, T. A.; Lynn, D. M.; Grubbs, R. H. J. Org. Chem. 1998, 63, 9904.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 3115
    • Hanessian, S.1    Leger, R.2
  • 72
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    • Varian Associates, Inc.: Palo Alto, CA
    • VNMR 6.1B Software; Varian Associates, Inc.: Palo Alto, CA, 2001.
    • (2001) VNMR 6.1B Software
  • 73
    • 0041679098 scopus 로고    scopus 로고
    • Crystallographic information files (CIFs) for 2, 7, and 9 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC 161995, 174072, and 167560, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK. Fax: +44 1223 336033. E-mail: deposit@ccdc.cam.ac.uk). Structure factors are available from the authors via e-mail: xray@caltech.edu.
  • 74
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    • Bruker AXS, Inc.: Madison, WI
    • SMART, SAINT, and SHELXTL; Bruker AXS, Inc.: Madison, WI, 1999.
    • (1999) SMART, SAINT, and SHELXTL


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.