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Volumn 347, Issue 1, 2005, Pages 161-171

Evidence that SCS pincer Pd(II) complexes are only precatalysts in Heck catalysis and the implications for catalyst recovery and reuse

Author keywords

Biphasic catalysis; Heck reaction; Immobilization; Leaching; Palladium; Pincer complex

Indexed keywords

ACRYLIC ACID BUTYL ESTER; AMIDE; IODOBENZENE; NORBORNENE DERIVATIVE; PALLADIUM COMPLEX; POLY(NORBORNENE); POLYMER; RESIN; SILICON DIOXIDE; UNCLASSIFIED DRUG; UREA;

EID: 14644438518     PISSN: 16154150     EISSN: None     Source Type: Journal    
DOI: 10.1002/adsc.200404264     Document Type: Article
Times cited : (305)

References (87)
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    • Here we use the traditional definitions of homogeneous (soluble) and heterogeneous (insoluble) catalysts. The alternative definitions (homogeneous - single-site and heterogeneous - multi-site) introduced by a) J. Schwartz, Acc. Chem. Res. 1985, 18, 302; and refined by b) Y. Lin, R. G. Finke, Inorg. Chem. 1994, 33, 4891; c) J. D. Aiken, Y. Lin, R. G. Finke, J. Mol. Catal. A. 1996, 114, 29 are not used.
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    • Here we use the traditional definitions of homogeneous (soluble) and heterogeneous (insoluble) catalysts. The alternative definitions (homogeneous - single-site and heterogeneous - multi-site) introduced by a) J. Schwartz, Acc. Chem. Res. 1985, 18, 302; and refined by b) Y. Lin, R. G. Finke, Inorg. Chem. 1994, 33, 4891; c) J. D. Aiken, Y. Lin, R. G. Finke, J. Mol. Catal. A. 1996, 114, 29 are not used.
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    • Lin, Y.1    Finke, R.G.2
  • 3
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    • are not used
    • Here we use the traditional definitions of homogeneous (soluble) and heterogeneous (insoluble) catalysts. The alternative definitions (homogeneous - single-site and heterogeneous - multi-site) introduced by a) J. Schwartz, Acc. Chem. Res. 1985, 18, 302; and refined by b) Y. Lin, R. G. Finke, Inorg. Chem. 1994, 33, 4891; c) J. D. Aiken, Y. Lin, R. G. Finke, J. Mol. Catal. A. 1996, 114, 29 are not used.
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    • Aiken, J.D.1    Lin, Y.2    Finke, R.G.3
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    • g) R. B. Bedford, C. S. J. Cazin, M. B. Hursthouse, M. E. Light, K. J. Pike, S. Wimperis, J. Organomet. Chem. 2001, 633, 173; also, for PCP pincer complexes: M. R. Eberhard, Org. Lett. 2004, 6, 2125.
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    • Eberhard, M.R.1
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    • the mechanism was previously ruled out for half-pincer complexes: e) V. P. W. Bohm, W. A. Herrmann, Chem. Eur. J. 2001, 7, 4191; f) J. A. Loch, M. Albrecht, E. Peris, J. Mata, J. W. Faller, R. H. Crabtree, Organometallics 2002, 21, 700; g) H. Nakai, S. Ogo, Y. Watanabe, Organometallics 2002, 21, 1674.
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    • Bohm, V.P.W.1    Herrmann, W.A.2
  • 62
    • 0000709581 scopus 로고    scopus 로고
    • the mechanism was previously ruled out for half-pincer complexes: e) V. P. W. Bohm, W. A. Herrmann, Chem. Eur. J. 2001, 7, 4191; f) J. A. Loch, M. Albrecht, E. Peris, J. Mata, J. W. Faller, R. H. Crabtree, Organometallics 2002, 21, 700; g) H. Nakai, S. Ogo, Y. Watanabe, Organometallics 2002, 21, 1674.
    • (2002) Organometallics , vol.21 , pp. 700
    • Loch, J.A.1    Albrecht, M.2    Peris, E.3    Mata, J.4    Faller, J.W.5    Crabtree, R.H.6
  • 63
    • 0013309970 scopus 로고    scopus 로고
    • the mechanism was previously ruled out for half-pincer complexes: e) V. P. W. Bohm, W. A. Herrmann, Chem. Eur. J. 2001, 7, 4191; f) J. A. Loch, M. Albrecht, E. Peris, J. Mata, J. W. Faller, R. H. Crabtree, Organometallics 2002, 21, 700; g) H. Nakai, S. Ogo, Y. Watanabe, Organometallics 2002, 21, 1674.
    • (2002) Organometallics , vol.21 , pp. 1674
    • Nakai, H.1    Ogo, S.2    Watanabe, Y.3
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    • note
    • [10] the precatalysts are extensively washed and extracted in hot solvents to insure that physisorbed species are removed from the materials before they are used in Heck reactions.
  • 75
    • 14644394457 scopus 로고    scopus 로고
    • note
    • We note that the temperatures and solvents used in the acid-catalyzed dimerization and in the Heck reaction are different. However, we have confirmed that PVPy is largely insoluble in DMF at reaction temperature using the following test. PVPy was heated in DMF at the reaction temperature for 30 min. The PVPy was subsequently removed by filtration and the remaining liquid was used as the solvent for a Heck reaction with added 1. The kinetics of this reaction were unchanged compared to standard conditions using 1 as the precatalyst. Thus, there was no appreciable soluble PVPy in solution.
  • 76
    • 14644406394 scopus 로고    scopus 로고
    • note
    • With limited characterizations on material 6 (characterized by FT-Raman). we are not able to confirm that only the SCS-Pd pincer (with a Pd-C bond) was formed, and it is possible that small amount of coordination complex that does not have a Pd-C bond is formed during palladation.
  • 78
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    • Texas A&M University, College Station, TX
    • b) J. D. Frels, Ph. D. Dissertation 2002, Texas A&M University, College Station, TX.
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    • [14]
    • [14]
  • 84
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    • note
    • TEM images of the precursor complex 1 and the reaction solution were taken in an attempt to document potential nanoparticle formation (Pd black formation was documented visually in the reaction solution). However, the data proved to be inconclusive.
  • 85
    • 3142760135 scopus 로고    scopus 로고
    • [9a,10] imply that other Pd(II)-SCS complexes that are claimed to be recyclable and recoverable likely also decompose: D. P. Curran, K. Fischer, G. Moura-Letts, Synlett 2004, 1379.
    • (2004) Synlett , pp. 1379
    • Curran, D.P.1    Fischer, K.2    Moura-Letts, G.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.